Thin-film batteries with polymer and LiPON electrolyte layers and method

ABSTRACT

A method and apparatus for making thin-film batteries having composite multi-layered electrolytes with soft electrolyte between hard electrolyte covering the negative and/or positive electrode, and the resulting batteries. In some embodiments, foil-core cathode sheets each having a cathode material (e.g., LiCoO 2 ) covered by a hard electrolyte on both sides, and foil-core anode sheets having an anode material (e.g., lithium metal) covered by a hard electrolyte on both sides, are laminated using a soft (e.g., polymer gel) electrolyte sandwiched between alternating cathode and anode sheets. A hard glass-like electrolyte layer obtains a smooth hard positive-electrode lithium-metal layer upon charging, but when very thin, have randomly spaced pinholes/defects. When the hard layers are formed on both the positive and negative electrodes, one electrode&#39;s dendrite-short-causing defects on are not aligned with the other electrode&#39;s defects. The soft electrolyte layer both conducts ions across the gap between hard electrolyte layers and fills pinholes.

CROSS-REFERENCE TO RELATED APPLICATIONS

This invention is a divisional of U.S. Ser. No. 11/458,093, filed Jul.17, 2006, now U.S. Pat. No. 7,776,478 by Klaassen, entitled “THIN-FILMBATTERIES WITH POLYMER AND LIPON ELECTROLYTE LAYERS AND METHOD,” whichclaims benefit of U.S. Provisional Patent Application 60/699,895 filedJul. 15, 2005, which is hereby incorporated by reference in itsentirety. This is also related to U.S. patent application 10/895,445entitled “LITHIUM/AIR BATTERIES WITH LiPON AS SEPARATOR AND PROTECTIVEBARRIER AND METHOD” filed Oct. 16, 2003 by J. Klaassen, the inventor ofthe present application, and to U.S. patent application Ser. No.11/031,217 entitled “LAYERED BARRIER STRUCTURE HAVING ONE OR MOREDEFINABLE LAYERS AND METHOD” filed Jan. 6, 2005, U.S. patent applicationSer. No. 11/458,091, entitled “THIN-FILM BATTERIES WITH SOFT AND HARDELECTROLYTE LAYERS AND METHOD”and U.S. patent application Ser. No.11,458,097, entitled “APPARATUS AND METHOD FOR MAKING THIN-FILMBATTERIES WITH SOFT AND HARD ELECTROLYTE LAYERS”filed on Jul. 17, 2006,which are all incorporated herein in their entirety by reference.

FIELD OF THE INVENTION

This invention relates to solid-state energy-storage devices, and morespecifically to a method and apparatus for making thin-film (e.g.,lithium) battery devices with a soft (e.g., polymer) electrolyte layer,and one or more hard layers (e.g., LiPON) as electrolyte layer(s) and/orprotective barrier(s), and the resulting cell(s) and/or battery(s).

BACKGROUND OF THE INVENTION

Electronics have been incorporated into many portable devices such ascomputers, mobile phones, tracking systems, scanners, and the like. Onedrawback to portable devices is the need to include the power supplywith the device. Portable devices typically use batteries as powersupplies. Batteries must have sufficient capacity to power the devicefor at least the length of time the device is in use. Sufficient batterycapacity can result in a power supply that is quite heavy and/or largecompared to the rest of the device. Accordingly, smaller and lighterbatteries (i.e., power supplies) with sufficient energy storage aredesired. Other energy storage batteries (i.e., power supplies) withsufficient energy storage are desired. Other energy storage devices,such as supercapacitors, and energy conversion devices, such asphotovoltaics and fuel cells, are alternatives to batteries for use aspower supplies in portable electronics and non-portable electricalapplications.

Another drawback of conventional batteries is the fact that some arefabricated from potentially toxic materials that may leak and be subjectto governmental regulation. Accordingly, it is desired to provide anelectrical power source that is safe, solid-state and rechargeable overmany charge/discharge life cycles.

One type of an energy-storage device is a solid-state, thin-filmbattery. Examples of thin-film batteries are described in U.S. Pat. Nos.5,314,765; 5,338,625; 5,445,906; 5,512,147; 5,561,004; 5,567,210;5,569,520; 5,597,660; 5,612,152; 5,654,084; and 5,705,293, each of whichis herein incorporated by reference. U.S. Pat. No. 5,338,625 describes athin-film battery, especially a thin-film microbattery, and a method formaking same having application as a backup or first integrated powersource for electronic devices. U.S. Pat. No. 5,445,906 describes amethod and system for manufacturing a thin-film battery structure formedwith the method that utilizes a plurality of deposition stations atwhich thin battery component films are built up in sequence upon aweb-like substrate as the substrate is automatically moved through thestations.

U.S. Pat. No. 6,805,998 entitled “METHOD AND APPARATUS FOR INTEGRATEDBATTERY DEVICES” (which is incorporated herein by reference) issued Oct.19, 2004, by Mark L. Jenson and Jody J. Klaassen (the inventor of thepresent application), and is assigned to the assignee of the presentinvention, described a high-speed low-temperature method for depositingthin-film lithium batteries onto a polymer web moving through a seriesof deposition stations.

K. M. Abraham and Z. Jiang, (as described in U.S. Pat. No. 5,510,209,which is incorporated herein by reference) demonstrated a cell with anon-aqueous polymer separator consisting of a film of polyacrylonitrileswollen with a propylene carbonate/ethylene carbonate/LiPF₆ electrolytesolution. This organic electrolyte membrane was sandwiched between alithium metal foil anode and a carbon composite cathode to form thelithium-air cell. The utilization of the organic electrolyte allowedgood performance of the cell in an oxygen or dry air atmosphere.

As used herein, the anode of the battery is the positive electrode(which is the anode during battery discharge) and the cathode of thebattery is the negative electrode (which is the cathode during batterydischarge). (During a charge operation, the positive electrode is thecathode and the negative electrode is the anode, but the anode-cathodeterminology herein reflects the discharge portion of the cycle.)

U.S. Pat. No. 6,605,237 entitled “Polyphosphazenes as gel polymerelectrolytes” (which is incorporated herein by reference), issued toAllcock, et al. on Aug. 12, 2003, and describes co-substituted linearpolyphosphazene polymers that could be useful in gel polymerelectrolytes, and which have an ion conductivity at room temperature ofat least about 10⁻⁵ S/cm and comprising (i) a polyphosphazene havingcontrolled ratios of side chains that promote ionic conductivity andhydrophobic, non-conductive side chains that promote mechanicalstability, (ii) a small molecule additive, such as propylene carbonate,that influences the ionic conductivity and physical properties of thegel polymer electrolytes, and (iii) a metal salt, such as lithiumtrifluoromethanesulfonate, that influences the ionic conductivity of thegel polymer electrolytes, and methods of preparing the polyphosphazenepolymers and the gel polymer electrolytes. Allcock et al. discuss asystem that has been studied extensively for solid-polymer electrolyte(SPE) applications, which is one that is based onpoly(organophosphazenes). This class of polymers has yielded excellentcandidates for use in SPEs due to the inherent flexibility of thephosphorus-nitrogen backbone and the ease of side group modification viamacromolecular substitution-type syntheses. The firstpoly(organophosphazene) to be used in a phosphazene SPE (solid polymerelectrolyte) was poly[bis(2-(2′-methoxyethoxy ethoxy)phosphazene](hereinafter, MEEP). This polymer was developed in 1983 by Shriver,Allcock and their coworkers (Blonsky, P. M., et al, Journal of theAmerican Chemical Society, 106, 6854 (1983)) and is illustrated in U.S.Pat. No. 6,605,237.

Also, the following U.S. Pat. No. 7,052,805 (Polymer electrolyte havingacidic, basic and elastomeric subunits, published/issued on 2006 May30); U.S. Pat. No. 6,783,897 (Crosslinking agent and crosslinkable solidpolymer electrolyte using the same, 2004 Aug. 31); U.S. Pat. No.6,727,024 (Polyalkylene oxide polymer composition for solid polymerelectrolytes, 2004 Apr. 27); U.S. Pat. No. 6,392,008 (Polyphosphazenepolymers, 2002 May 21); U.S. Pat. No. 6,369,159 (Antistatic plasticmaterials containing epihalohydrin polymers, 2002 Apr. 9); U.S. Pat. No.6,214,251 (Polymer electrolyte composition, 2001 Apr. 10); U.S. Pat. No.5,998,559 (Single-ion conducting solid polymer electrolytes, andconductive compositions and batteries made therefrom; 1999 Dec. 7); U.S.Pat. No. 5,874,184 (Solid polymer electrolyte, battery and solid-stateelectric double layer capacitor using the same as well as processes forthe manufacture thereof, 1999 Feb. 23); U.S. Pat. No. 5,698,664(Synthesis of polyphosphazenes with controlled molecular weight andpolydispersity, 1997 Dec. 16); U.S. Pat. No. 5,665,490 (Solid polymerelectrolyte, battery and solid-state electric double layer capacitorusing the same as well as processes for the manufacture thereof, 1997Sep. 9); U.S. Pat. No. 5,633,098 (Batteries containing single-ionconducting solid polymer electrolytes, 1997 May 27); U.S. Pat. No.5,597,661 (Solid polymer electrolyte, battery and solid-state electricdouble layer capacitor using the same as well as processes for themanufacture thereof, 1997 Jan. 28); U.S. Pat. No. 5,567,783(Polyphosphazenes bearing crown ether and related podand side groups assolid solvents for ionic conduction, 1996 Oct. 22); U.S. Pat. No.5,562,909 (Phosphazene polyelectrolytes as immunoadjuvants, 1996 Oct.8); U.S. Pat. No. 5,548,060 (Sulfonation of polyphosphazenes, 1996 Aug.20); U.S. Pat. No. 5,414,025 (Method of crosslinking of solid statebattery electrolytes by ultraviolet radiation, 1995 May 9); U.S. Pat.No. 5,376,478 (Lithium secondary battery of vanadium pentoxide andpolyphosphazenes, 1994 Dec. 27); U.S. Pat. No. 5,219,679 (Solidelectrolytes, 1993 Jun. 15); U.S. Pat. No. 5,110,694 (Secondary Libattery incorporating 12-Crown-4 ether, 1992 May 5); U.S. Pat. No.5,102,751 (Plasticizers useful for enhancing ionic conductivity of solidpolymer electrolytes, 1992 Apr. 7); U.S. Pat. No. 5,061,581 (Novel solidpolymer electrolytes, 1991 Oct. 29); U.S. Pat. No. 4,656,246(Polyetheroxy-substituted polyphosphazene purification, 1987 Apr. 7);and U.S. Pat. No. 4,523,009, (Polyphosphazene compounds and method ofpreparation, 1985 Jun. 11), which are all incorporated herein byreference. Each discuss polyphosphazene polymers and/or other polymerelectrolytes and/or lithium salts and combinations thereof

U.S. patent application Ser. No. 10/895,445 entitled “LITHIUM/AIRBATTERIES WITH LiPON AS SEPARATOR AND PROTECTIVE BARRIER AND METHOD” bythe inventor of the present application (which is incorporated herein byreference) describes a method for making lithium batteries includingdepositing UPON on a conductive substrate (e.g., a metal such as copperor aluminum) by depositing a chromium adhesion layer on an electricallyinsulating layer of silicon oxide by vacuum sputter deposition of 50 nmof chromium followed by 500 nm of copper. In some embodiments, a thinfilm of LiPON (Lithium Phosphorous OxyNitride) is then formed bylow-pressure (<10 mtorr) sputter deposition of lithium orthophosphate(Li₃PO₄) in nitrogen. In some embodiments of the Li-air battery cells,LiPON was deposited over the copper anode current-collector contact to athickness of 2.5 microns, and a layer of lithium metal was formed ontothe copper anode current-collector contact by electroplating through theLiPON layer in a propylene carbonate/LiPF₆ electrolyte solution. In someembodiments, the air cathode was acarbon-powder/polyfluoroacrylate-binder coating (Novec-1700) saturatedwith a propylene carbonate/LiPF₆ organic electrolyte solution. In otherembodiments, a cathode-current-collector contact layer having carbongranules is deposited, such that atmospheric oxygen could operate as thecathode reactant. This configuration requires providing air access tosubstantially the entire cathode surface, limiting the ability todensely stack layers for higher electrical capacity (i.e., amp-hours).

There is a need for rechargeable lithium-based batteries having improvedprotection against dendrite formation and with improved density,electrical capacity, rechargeability, and reliability, and smallervolume and lowered cost.

BRIEF SUMMARY OF THE INVENTION

In some embodiments, the present invention includes a battery having anelectrolyte structure that combines a plurality of layers of differentelectrolytes (e.g., hard-soft-hard). In some embodiments, a thin (0.1 to1.0 micron) LiPON electrolyte layer serves as a hard coating on thenegative electrode preventing the formation of lithium dendrites(especially when paired with a corresponding LiPON electrolyte layercoating on the positive electrode) and/or providing an even (smooth),hard layer of lithium metal on, or as part of, the negative electrodewhen the battery is charged. In some embodiments, a thin (0.1 to 1.0micron) LiPON electrolyte on only one electrode (e.g., the negativeelectrode) may not prevent the formation of lithium dendrites over thelong term (e.g., many thousands of discharge-recharge cycles), since thelithium growing through a pinhole may only need to grow about 3 micronsor less across the electrolyte to short the battery (i.e., providing ametal electrical conduction path directly from anode to cathode). WhenLiPON is also used as a coating at the positive electrode (e.g., anelectrode that includes LiCoO₂) the random locations of the pinholeswill not line up (e.g., across the electrolyte from anode to cathode) solithium would also need to grow sideways in the electrolyte, whichdoubly ensures that lithium plating at a defect site (which wouldtypically form a dendrite) will not short the battery. In someembodiments, a soft electrolyte layer bridges the gap between the hardelectrolyte layer on the negative electrode and the hard electrolytelayer on the positive electrode. At both electrodes, the LiPON layeralso provides an improvement in environmental resistance to water vaporand oxygen, especially during manufacture before the battery iscompleted and otherwise sealed. In some embodiments, the softelectrolyte includes a solid polymer electrolyte (SPE) layer that islocated between and contacts with the LiPON layer on the positiveelectrode and the LiPON layer on the negative electrode. In someembodiments, the electrolyte structure includes a polymer electrolytesuch as PEO-LiX (poly-ethylene oxide lithium-X, where LiX=a metal salt,such as LiPF6, LiBF₄, LiCF₃SO₄, CF₃SO₃Li (lithiumtrifluoromethanesulfonate, also called triflate), lithiumbisperfluoroethanesulfonimide, lithium (Bis)Trifluoromethanesulfonimide, and/or the like, for example). In someembodiments, the electrolyte structure includes a polymer electrolytesuch as polyPN-LiX (Polyphosphazene with lithium-X, where LiX═LiPF₆,LiBF₄, LiCF₃SO₄, and/or the like, for example). In some embodiments, asmall-molecule additive, such as propylene carbonate, that influencesthe ionic conductivity and physical properties of the polymerelectrolytes is added to form a gel electrolyte that better fillsdefects and acts as an adhesive.

The present invention provides both a method and an apparatus for makingthin-film batteries having composite (e.g., multi-layered) electrolyteswith a soft electrolyte layer between hard electrolyte layers coveringthe negative and/or positive electrodes, and the resulting batteries. Insome embodiments, metal-core cathode sheets each having a cathodematerial (e.g., LiCoO2) deposited on a metal foil, screen, or mesh(e.g., copper, nickel, or stainless steel) or a metal-covered insulator(e.g., a sputtered metal film on a polymer film, a SiO2-covered siliconwafer, or an alumina or sapphire substrate) and is covered by a hardelectrolyte (some embodiments form such electrodes on both sides of thesubstrate), and foil-core anode sheets having a anode material (e.g.,lithium metal) deposited on a metal foil (e.g., copper, nickel, orstainless steel) or a metal-covered insulator (e.g., a sputtered metalfilm on a polymer film, a SiO2-covered silicon wafer, or an alumina orsapphire substrate) and is also covered by a hard electrolyte (someembodiments form such electrodes on both sides of the substrate), andsuch sheets are laminated using a soft (e.g., polymer gel) electrolytesandwiched between alternating cathode and anode sheets. In someembodiments, a hard glass-like electrolyte layer obtains a smooth hardpositive-electrode lithium-metal layer upon charging, but when such alayer is made very thin, will tend to have randomly spacedpinholes/defects. When the hard layers are formed on both the positiveand negative electrodes, one electrode's dendrite-short-causing defectson are not aligned with the other electrode's defects. The softelectrolyte layer conducts ions across the gap between hard electrolytelayers and/or fills pinholes, thin spots, and other defects in the hardelectrolyte layers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a schematic cross-section view of a lithium cell 100 of someembodiments of the invention.

FIG. 1B is a schematic cross-section view of a lithium cell 101 of someembodiments of the invention.

FIG. 1C is a schematic cross-section view of a lithium cell 102 of someembodiments of the invention.

FIG. 2 is a schematic cross-section view of a lithium-batterymanufacturing process 200 of some embodiments of the invention.

FIG. 3 is a schematic cross-section view of a parallel-connected lithiumbattery 300 of some embodiments of the invention.

FIG. 4 is a schematic cross-section view of a series-connected lithiumbattery 400 of some embodiments of the invention.

FIG. 5A is a schematic cross-section view of a parallel-connectedscreen-cathode current-collector contact lithium-battery 500 of someembodiments of the invention.

FIG. 5B is a schematic cross-section view of a series-connectedscreen-cathode-current-collector contact lithium-battery 501 of someembodiments of the invention.

FIG. 6A is a perspective view of an electrode 600 having ahard-electrolyte-covered current collector with a plating mask 119.

FIG. 6B is a perspective view of another electrode 601 having ahard-electrolyte-covered current collector with a plating mask 119.

FIG. 6C is a perspective view of a plating system 610.

FIGS. 7A, 7B, 7C, 7D, 7E, and 7F are schematic cross-sectional views ofthe fabrication of an atomic level matrix of copper and copper oxides ascathodes on a substrate of some embodiments of the invention.

FIGS. 8A, 8B, 8C, 8D, and 8E are schematic cross-sectional views of thefabrication of an atomic level matrix of copper and copper oxides ascathodes on a copper foil substrate of some embodiments of theinvention.

FIG. 9 is a schematic cross-section view of a parallel-connectedfoil-cathode-current-collector contact lithium battery 900 of someembodiments of the invention.

FIG. 10A is a schematic cross-section view of an encapsulatedsurface-mount micro-battery 1000 of some embodiments of the invention.

FIG. 10B is a perspective view of an encapsulated surface-mountmicro-battery 1000 of some embodiments of the invention.

FIG. 11 is a flow chart of a method 1100 for making a battery cellaccording to some embodiments of the invention.

FIG. 12 is a flow chart of a method 1200 for making a stacked batteryaccording to some embodiments of the invention.

FIG. 13 is an exploded perspective view of an embodiment of a device aspart of a system.

FIG. 14 is an exploded perspective view of another embodiment of adevice as part of a portable system.

DETAILED DESCRIPTION OF THE INVENTION

Although the following detailed description contains many specifics forthe purpose of illustration, a person of ordinary skill in the art willappreciate that many variations and alterations to the following detailsare within the scope of the invention. Accordingly, the followingpreferred embodiments of the invention are set forth without any loss ofgenerality to, and without imposing limitations upon the claimedinvention.

In the following detailed description of the preferred embodiments,reference is made to the accompanying drawings that form a part hereof,and in which are shown by way of illustration specific embodiments inwhich the invention may be practiced. It is understood that otherembodiments may be utilized and structural changes may be made withoutdeparting from the scope of the present invention.

The leading digit(s) of reference numbers appearing in the Figuresgenerally correspond to the Figure number in which that component isfirst introduced, such that the same reference number is used throughoutto refer to an identical component, which appears in multiple Figures.Signals (such as, for example, fluid pressures, fluid flows, orelectrical signals that represent such pressures or flows), pipes,tubing or conduits that carry the fluids, wires or other conductors thatcarry the electrical signals, and connections may be referred to by thesame reference number or label, and the actual meaning will be clearfrom its use in the context of the description.

Terminology

In this description, the term metal applies both to substantially puresingle metallic elements and to alloys or combinations of two or moreelements, at least one of which is a metallic element.

The term substrate or core generally refers to the physical structurethat is the basic work piece that is transformed by various processoperations into the desired microelectronic configuration. In someembodiments, substrates include conducting material (such as copper,stainless steel, aluminum and the like), insulating material (such assapphire, ceramic, or plastic/polymer insulators and the like),semiconducting materials (such as silicon), non-semiconducting, orcombinations of semiconducting and non-semiconducting materials. In someother embodiments, substrates include layered structures, such as a coresheet or piece of material (such as iron-nickel alloy and the like)chosen for its coefficient of thermal expansion (CTE) that more closelymatches the CTE of an adjacent structure such as a silicon processorchip. In some such embodiments, such a substrate core is laminated to asheet of material chosen for electrical and/or thermal conductivity(such as a copper, aluminum alloy and the like), which in turn iscovered with a layer of plastic chosen for electrical insulation,stability, and embossing characteristics. An electrolyte is a materialthat conducts electricity by allowing movement of ions (e.g., lithiumions having a positive charge) while being non-conductive or highlyresistive to electron conduction. An electrical cell or battery is adevice having an anode and a cathode that are separated by anelectrolyte. A dielectric is a material that is non-conducting toelectricity, such as, for example, plastic, ceramic, or glass. In someembodiments, a material such as LiPON can act as an electrolyte when asource and sink for lithium are adjacent the LiPON layer, and can alsoact as a dielectric when placed between two metal layers such as copperor aluminum, which do not form ions that can pass through the LiPON. Insome embodiments, devices include an insulating plastic/polymer layer (adielectric) having wiring traces that carry signals and electrical powerhorizontally, and vias that carry signals and electrical powervertically between layers of traces.

In some embodiments, an anode portion of a thin-film solid-state batteryis made (as described in U.S. patent application Ser. No. 10/895,445discussed above) using a method that includes depositing LiPON on aconductive substrate (e.g., a metal such as copper or aluminum) that isformed by depositing a chromium adhesion layer on an electricallyinsulating layer of silicon oxide (or on a polymer sheet) usingvacuum-sputter deposition of 50 nm of chromium followed by 500 nm ofcopper. In some embodiments, a thin film of LiPON (Lithium PhosphorousOxyNitride) is then formed by low-pressure (<10 mtorr) sputterdeposition of lithium orthophosphate (Li₃PO₄) in nitrogen, or bysputtering from a LiPON source. In some embodiments LiPON is depositedover the copper anode current-collector contact to a thickness ofbetween 0.1 microns and 2.5 microns. In some embodiments, a layer oflithium metal is formed onto the copper anode current-collector contactby electroplating through the LiPON layer (which was earlier depositedon the copper anode current-collector contact) in a propylenecarbonate/LiPF₆ organic electrolyte solution. The LiPON acts as aprotective layer during fabrication of the battery, and in the assembledbattery, it operates as one layer of a multi-layer electrolyte. (Inother embodiments, the layer of lithium metal of the anode is formed byan initial charging operation after the battery is assembled.) In someembodiments, a cathode portion of the thin-film solid-state battery ismade sputtering LiCoO₂ onto a first of metal foil from a LiCoO₂ source,over which is deposited a LiPON layer, which in the assembled battery,operates as another layer of the multi-layer electrolyte. In someembodiments, a solid or gel polymer electrolyte is used as a structuralconnection or adhesive between the two LiPON electrolyte layers, as wellas forming an ion-conductive path between the positive and negativeelectrodes of the battery.

It is desirable, in some embodiments, to form a very thin electrolyte.If a single very thin layer of LiPON is used, it tends to have defects(e.g., thin spots or pinholes) and lithium ions will preferentiallytravel through these paths of least resistance and plate to spike-shapedlithium-metal dendrites that short out the battery. If a single verythin solid or gel polymer electrolyte layer is used, any surfaceirregularities (e.g., bumps or ridges in the anode or cathode material)will tend to connect through the electrolyte and short the battery. Byhaving two independently formed very thin LiPON (hard) electrolytecomponent layers, one formed on the battery's anode and another formedon the battery's cathode, any such thin spots or pinholes in one layerwill not line up with a thin spot or pinhole in the other layer. Thethird electrolyte layer (e.g., a soft polymer electrolyte that conductslithium ions between the two LiPON layers) made of a solid and/or gelpolymer electrolyte material does not get shorted out by bumps or otherirregularities in either electrode since those irregularities will tendto be coated with LiPON and/or the corresponding spot on the other sidewill be coated with LiPON. Accordingly, one or more (even all) of theplurality of layers can be made very thin without the danger of havingan initial short (from a polymer electrolyte that is too thin allowingthe anode and cathode to touch) or a later-developed short (from apinhole in a LiPON electrolyte layer that allows formation of alithium-metal dendrite after one or more charge/discharge cycles).Further, the dense, hard, glass-like LiPON layer causes the lithium ionsthat pass through it to form a lithium-metal layer that is dense andsmooth. In other embodiments, one or more other hard and/or glass-likeelectrolyte layers are used instead of one or more of the LiPON layers.

U.S. Pat. No. 6,605,237 entitled “Polyphosphazenes as gel polymerelectrolytes” discusses MEEP (poly[bis(2-(2′-methoxyethoxyethoxy)phosphazene]) and other polymers, which are used in someembodiments of the present invention as structural connector and polymerelectrolyte sublayer between two UPON sublayers. The polyphosphazene(herein called polyPN) used as the connective layer is soft and sticky.Its adhesive properties are what allow the electrode to be and to remainjoined. Its softness allows for defect correction and/or for defects tonot cause poor battery performance and reliability. In otherembodiments, other soft or gel-like ion-conducting polymers are used.

U.S. Pat. Nos. 4,523,009, 5,510,209, 5,548,060, 5,562,909, 6,214,251,6,392,008 6,605,237, and 6,783,897 (which are all incorporated herein byreference) each discuss polyphosphazene polymers and/or other polymerelectrolytes and/or various lithium salts and compounds that can be usedas, or included in, one or more component layers of an electrolyte insome embodiments of the present invention.

The term vertical is defined to mean substantially perpendicular to themajor surface of a substrate. Height or depth refers to a distance in adirection perpendicular to the major surface of a substrate.

FIG. 1A is a schematic cross-section view of a lithium cell 100 of someembodiments of the invention. In some embodiments, cell 100 includes afirst sheet 111 (a cathode or positive-electrode subassembly) having afirst metal foil 110 (which acts as a current collector) onto which isdeposited a film of cathode material 112, such as, for example, LiCoO₂,for example, by sputtering from a LiCoO₂ target, and over which isdeposited a relatively hard LiPON layer 114 (which acts as ahard-electrolyte current spreader). In some embodiments, cell 100includes a second sheet 121 (an anode or negative-electrode subassembly)having a second metal foil 120 (which acts as a current collector) ontowhich is deposited a film of LiPON 124 (which acts as a hard-electrolytecurrent spreader and as an environmental barrier for lithium that islater plated through this layer), and a layer of lithium 122 (whichforms the active portion of the anode or negative-electrode) is platedthrough the LiPON film 124 (either before or after the entire battery isassembled: if the cathode contains sufficient lithium to start, then theanode lithium layer is formed after assembly by the initial charging ofthe battery, while if the cathode has little or no lithium to startwith, then the anode lithium layer is formed before assembly, e.g., byelectroplating in a liquid electrolyte or solution from an externalsacrificial lithium-metal electrode). In some embodiments, a sheet orlayer of polymer electrolyte 130 is sandwiched between the first sheet111 and the second sheet 121. In some embodiments, the layer of thepolymer electrolyte is deposited onto LiPON layer 114, LiPON layer 124,or a portion of the polymer electrolyte is deposited onto both LiPONlayer 114 and LiPON layer 124, and then the first sheet 111 and thesecond sheet 121 are pressed together or otherwise assembled (in someembodiments, two or more of the sheets are squeezed together between apair of rollers).

In some embodiments, it is the hard-soft-hard combination of electrolytelayers that provide a low-cost, high-quality, high-reliability, highlyrechargeable battery system. In some embodiments, the hard layers act asprotective barrier layers during manufacture and as current spreaderelectrolytes that obtain a smooth hard layer of lithium on the anodeupon charging. In some embodiments, the hard layers are or include aglass or glass-like electrolyte material (e.g., LiPON). When they aremade very thin (in order to increase cell conductivity and reduce cellresistance), these hard layers tend to have randomly spaced pinholes,bumps, or other defects (thicker layers can eliminate many such defects,but will have decreased cell conductivity and increased cellresistance). When the hard layers are formed on both the positiveelectrode and the corresponding negative electrode, the pinholes anddefects of the electrolyte covering one electrode will tend not to bealigned with the pinholes and defects of the electrolyte covering theother electrode. The soft electrolyte layer both conducts ions acrossthe gap between hard layers and tends to fill the pinholes and defectsof the hard electrolyte coverings. In some embodiments, the softelectrolyte layer can be a solid or gel polymer electrolyte (these alsoact as adhesives to hold the cells together and as seals to reducecontamination of the cell from environmental factors and to reduceleakage of the soft electrolyte layer), or can be a liquid electrolyte,optionally infused in a structural element (such as a sponge, screen, orridges formed of a host solid-polymer (e.g., polyethylene,polypropylene, fluoroethylene or the like) on one or more of the hardelectrolyte layers (e.g., by microembossing).

In some embodiments, the soft electrolyte layer includes a gel thatincludes a polyvinylidene difluoride (PVdF), propylene carbonate, and alithium salt. PVdF is a polymer that does not conduct lithium ions, thatis, lithium salts will not dissolve in PVdF. However, PVdF can beswollen with a liquid such as propylene carbonate in which a lithiumsalt has been dissolved. The gel that results can be used as a softelectrolyte.

In some embodiments, the thickness of each of the hard electrolytelayers is one micron or thinner, and the thickness of the softelectrolyte layer is about three microns or thinner. The structure shownin FIG. 1A is also represented in the following Table 1:

TABLE 1 Reference Function or Number Property Example Materials . . .optionally, more battery layers stacked above . . . 110 cathode metalfoil (e.g., one that does not alloy with current Li, such as copper,nickel, stainless steel and collector the like), metal screen, or metalfilm on polymer film or SiO₂ layer on Si wafer, (can have electrodeformed on both sides for battery stack) 112 cathode LiCoO₂ (sputtered orpowder-pressed in place), material carbon powder, CuO powder (any of theabove can be infused with polyPN electrolyte material to increaseconductivity and lithium transport), or atomic matrix of copper andcopper oxides (which, in some embodiments, includes a taperedcomposition Cu and O structure with more copper towards the top and moreoxygen towards the bottom, e.g., Cu metal gradually mixed to . . .Cu₄O.. .Cu₂O. . .Cu⁺O⁻⁻. . .CuO) 114 hard LiPON or electrolyte otherlithium-glass material 130 soft polyPN with lithium (e.g., LiPF₆), orother electrolyte polymer (e.g., PEO, polypropylene, etc.) electrolytematerial 124 hard LiPON or electrolyte other lithium-glass material 122anode Lithium, (can be plated through the hard material (e.g., LiPON)layer before or after assembly) (could be zinc with suitable changes toelectrolytes and cathode material) 110 anode metal foil (e.g., copper),metal screen, or current metal film on polymer film or SiO₂ layer on Sicollector wafer, (can have electrode formed on both sides for batterystack) . . . optionally, more battery layers stacked below

FIG. 1B is a schematic cross-section view of a lithium cell 101 of someembodiments of the invention. In some embodiments, cell 101, which isassembled in an uncharged state, includes a first sheet 111 (a cathodeor positive-electrode subassembly) similar to that of FIG. 1A, exceptthat the hard electrolyte 114 extends laterally over first metal foil110 well beyond the lateral edges of the film of cathode material 112.In some embodiments, the lateral extent of cathode material 112 (suchas, for example, LiCoO₂, for example) is defined using photoresist andlithographic processes similar to those used for semiconductorintegrated circuits (e.g., the cathode material is masked usingphotoresist, or a hard material such as SiO₂ covered by photoresist andetched and the photoresist is removed so that the hard layer (e.g.,SiO₂) acts as the mask, to define the lateral extent of cathode material112 (e.g., LiCoO₂), and the mask is then removed. The hard electrolytelayer 114 (e.g., LiPON) is deposited on the cathode material 112 as wellas onto substrate 110 around the sides of cathode material 112. Thissideward extension of the hard UPON layer 114 acts as a seal to thesides of the lithium in the cathode to protect it from environmentalcontaminants such as oxygen or water vapor. In some embodiments, cell101 includes a second sheet 121 (an anode or negative-electrodesubassembly similar to that of FIG. 1A, except that no lithium is yetpresent) having a second metal foil 120 (which acts as a currentcollector) onto which is deposited a film of LiPON 124 (which acts as ahard-electrolyte current spreader and as an environmental barrier forlithium that is later plated through this layer), and a mask layer 119around all of the sides of what will be plated lithium layer 122 (seeFIG. 1C) that is later plated through the portions of LiPON film 124 notcovered by mask 119 (after the entire battery is assembled). (In otherembodiments, mask layer 119 is an electrical insulator, such as SiO₂,deposited directly on metal foil 120, and photolithographicallypatterned to expose the metal substrate in the center, and the hardelectrolyte layer LiPON film 124 is deposited on top of the mask layer).In some embodiments, the mask material 119 is photoresist and/or aninsulator such as SiO₂ that have lateral extents that arephotolithographically defined. As above, in some embodiments, a layer ofsoft polymer electrolyte 130 (either a solid polymer electrolyte (SPE)or a gel or liquid polymer electrolyte) (such as polyphosphazene havinglithium salts such as LiPF₆ to assist lithium conductivity) issandwiched between the first sheet 111 and the second sheet 121.

FIG. 1C is a schematic cross-section view of a lithium cell 102 of someembodiments of the invention. In some embodiments, the lithium metallayer 122 is plated before assembly (a combination of the methodsdescribed for FIG. 6C and FIG. 2 below). In other embodiments, a battery101 (such as shown in FIG. 1B) is assembled before any lithium metal isin the anode assembly 121, and is initially charged by plating lithiumfrom the cathode 112 through electrolyte layers 114, 130, and 124 andonto the anode current collector 120 to form lithium metal layer 122.

FIG. 2 is a schematic cross-section view of a lithium-batterymanufacturing process 200 of some embodiments of the invention. In someembodiments, one or more double-sided anode sheets 121 are alternatedwith one or more cathode sheets 111 (wherein an cathode material 112 isdeposited on both major faces of foil 110 inside of LiPON layer 114),with a polymer layer 130 placed or formed between each sheet. In someembodiments of anode sheets 121, an anode material 122 is deposited onboth major faces of foil 120 inside of (or plated through) LiPON layer124 (note that, in some embodiments, by this stage, the mask 119 (seeFIG. 1B) has been removed from the lateral sides of the anode afterlithium metal has been pre-electro-plated through the LiPON not coveredby the mask 119 onto current collector 121 using a liquid electrolyteand a lithium sacrificial electrode.

In some embodiments, the soft polymer electrolyte layer 130 is spun onas a liquid and then dried. In other embodiments, the soft polymerelectrolyte layer 130 is dip coated. In other embodiments, the softpolymer electrolyte layer 130 is cast on. In some embodiments, the softpolymer electrolyte layer 130 is deposited from a liquid source 225,“squeegeed” (by squeegee 221) and/or doctor-bladed (by doctor-blade 222)in place onto both sides of each foil-core double-sided anode sheet 121(having previously had LiPON layer 124 and anode layer 122 formedthereon), and onto both sides of each foil-core double-sided cathodesheet 111 (having previously had cathode-material layer 112 and LiPONlayer 114 formed thereon). In some embodiments, the soft polymerelectrolyte layer 130 is deposited by an apparatus that is essentiallyan offset printing press, wherein a liquid soft polymer electrolytematerial and/or solvent mix (“ink”) is printed to the areas to which thesoft polymer electrolyte layer 130 is desired.), and the stack islaminated together (“calendared” e.g., by being pressed between rollers250 (for example, pressed between rubber-coated steel rollers, which, insome embodiments, are heated (e.g., by flowing hot oil inside therollers)). Note that rollers 250 are schematically shown relative to twocentral battery layers, where

In some embodiments, two or more such resulting stacks are thenlaminated together in a similar fashion. In other embodiments, all ofthe alternating layers of a battery device are laminated in a singlepressing step.

FIG. 3 is a schematic cross-section view of a parallel-connected lithiumbattery 300 of some embodiments of the invention, resulting from thelaminating method of FIG. 2. In some embodiments, the outermost layer111 and the outermost layer 121 are single sided, having a metal facefacing outwards. In other embodiments, all layers 111 are identical oneto another (and each is mirror-symmetrical about the center plane offoil 110), and all layers 121 are identical one to another (and each ismirror-symmetrical about the center plane of foil 120). In someembodiments, the edges of layers 111 are electrically connected to oneanother (for example, soldered, spot-welded or pressed together on theright-hand side) to form external cathode current-collector contact 321,and the edges of layers 121 are electrically connected to one another(for example, soldered, spot-welded or pressed together on the left-handside) to form external anode current-collector contact 322, thusconnecting all the cells in parallel to provide higher output current.In some embodiments, 1- to 30-mA-hour (or more) single cells are thusformed (depending on the area of each cell), and the battery has anamp-hour capacity of about the sum of the parallel cells.

TABLE 2 Materials List for FIG. 3 - 1 repeat unit Material ThicknessLayer Mass (microns) (mg/cm²) ½ cathode collector foil* 1.5 and up(e.g., 6.25) 4.94 Nickel seed 0.1 to 0.3 (e.g., 0.3) 0.27 LiCoO₂ 0.5 to10 (e.g., 5.0) 2.80 LiPON (cathode protect) 0.1 to 2.5 (e.g., 1.0) 0.21soft polymer electrolyte and/or 0.5 to 10 (e.g., 5.0) 0.75 “glue” LiPON(anode protect) 0.1 to 2.5 (e.g., 1.0) 0.21 Lithium (plated from LiCoO₂)about 0.3 times the 0.08 LiCoO₂ thickness (e.g., 1.5) Copper (or Al, Ni,stainless steel, 0.1 to 1 (e.g., 0.25) 0.22 and the like) (used as theLi plate surface) Anode collector foil 3.0 and up (e.g., 12.5) 9.88Copper (or Al, Ni, stainless steel, 0.1 to 1 (e.g., 0.25) 0.22 and thelike) (used as the Li plate surface) Lithium (plated from LiCoO₂) about0.3 times the 0.08 LiCoO₂ thickness (e.g., 1.5) LiPON (anode protect)0.1 to 2.5 (e.g., 1.0) 0.21 soft polymer electrolyte and/or 0.5 to 10(e.g., 5.0) 0.75 “glue” LiPON (cathode protect) 0.1 to 2.5 (e.g., 1.0)0.21 LiCoO₂ 0.5 to 10.0 (e.g., 5.0) 2.80 Nickel seed 0.1 to 0.3 (e.g.,0.3) 0.27 ½ cathode collector foil 1.5 and up (e.g., 6.25) 5.14 Totals(e.g., 53.1) 28.84 *In some embodiments, the foils are about 0.5-mils(0.0005 inches = 12.52-microns) thick

In some embodiments, the cathode material layers 112 are each about 10microns thick or more. In some embodiments, 10 microns of LiCoO₂provides about 0.552 mA-hour-per-square-cm per repeat unit 320 at 80%theoretical utilization, and 2.1 mW-hour-per-square-cm at3.8-volt-discharge voltage. In some embodiments, the charge-storagedensity is about 104 mA-hour/cubic-cm, and about 19.1 Ahour/kg. In someembodiments, the energy-storage density is about 395 W-hour/liter, andabout 72.8 W-hour/kg. In some embodiments, a 10-cm by 6.5-cm by onerepeat unit 320 corresponds to 33.6 mA-hour, and about 127 mW-hour. Insome embodiments, a final package measuring about 10.8-cm long by 6.5-cmwide by 1.8-cm thick houses three sets of 320 repeat units each, thesets tied in series to deliver 3.75 A-hour discharge from about 12.3volts to about 9 volts.

FIG. 4 is a schematic cross-section view of a series-connected lithiumbattery 400 of some embodiments of the invention. In the embodimentshown, each sheet 126 has anode material covered with LiPON on one majorface (the upper face in FIG. 4) of the foil 125, and cathode materialcovered with LiPON on the opposite major face (the lower face in FIG.4). In some embodiments, the outermost layers are single sided as shown,having a metal face facing outwards. In other embodiments, all layers125 are identical one to another, including the outermost layers. Insome embodiments, the edge of the top-most layer 125 is electricallyconnected (for example, on the right-hand side) to form external cathodecurrent-collector contact 421, and the edge of bottom-most layer 126 iselectrically connected (for example, on the left-hand side) to formexternal anode current-collector contact 422, thus connecting all thecells in series. Each repeat unit 420 shows one basic stack layer. Up toone-A-hour or more single cells are thus formed, in some embodiments,depending on the area of each cell.

FIG. 5A is a schematic cross-section view of a parallel-connectedscreen-cathode-current -collector contact lithium-battery 500 of someembodiments of the invention. This embodiment is substantially similarto that of FIG. 3, except that, for the positive electrode, a metalscreening or mesh 510 replaces foil 110. In some embodiments, thisallows greater contact area to the cathode material 112, which is stillcompletely covered by LiPON layer 114. In some embodiments, metalscreening or mesh 510 is formed by selectively etching one or morephoto-lithographically-defined areas of a metal foil. In someembodiments, LiCoO₂ is sputtered onto the metal screening 510. In otherembodiments, a LiCoO₂ powder is packed onto the screening 510. In someembodiments, the LiCoO₂ (whether deposited by sputtering LiCoO₂ or bypacking LiCoO₂ powder onto the screening 510) is infused with polyPN orother polymer electrolyte material to enhance the ionic conductivitywithin the cathode. In some embodiments, the screening 510 is initially(before depositing LiCoO₂) about 50% open space, and the open space isfilled with LiCoO₂ and/or polyPN or other ionic-enhancement material.

In some embodiments, the metal screening or mesh 510 of all of thelayers 511 are electrically connected to one another (for example, onthe right-hand side) to form external cathode current-collector contact521, and the edges of layers 120 are electrically connected to oneanother (for example, on the left-hand side) to form external anodecurrent-collector contact 522, thus connecting all the cells inparallel. Each repeat unit 520 shows one basic stack layer.

TABLE 3 Materials List for FIG. 5A - 1 repeat unit Material ThicknessLayer Mass (microns) (mg/cm²) ½ cathode collector 1.5 and up (e.g.,6.25) 2.59 screen/mesh/etched foil LiCoO₂ (cathode) 8.0 to 40 (e.g.,12.5) 7.00 LiPON (cathode protection and 0.1 to 2.5 (e.g., 1.0) 0.21electrolyte) soft polymer electrolyte and/or 0.5 to 10 (e.g., 5.0) 0.75“glue” LiPON (anode protection and 0.1 to 2.5 (e.g., 1.0) 0.21electrolyte) Lithium (plated from LiCoO₂) about 0.3 times 0.265 LiCoO₂thickness (e.g., 5.0) Copper (or Al, Ni, stainless steel, 0.1 to 1(e.g., 0.25) 0.22 and the like) (used as the Li plate surface) Anodecollector foil 3 and up (e.g., 12.5 9.88 Copper (or Al, Ni, stainlesssteel, 0.1 to 1 (e.g., 0.25) 0.22 and the like) (used as the Li platesurface) Lithium (plated from LiCoO₂) about 0.3 times 0.265 LiCoO₂thickness (e.g., 5.0) LiPON (anode protection and 0.1 to 2.5 (e.g., 1.0)0.21 electrolyte) soft polymer electrolyte and/or 0.5 to 10 (e.g., 5.0)0.75 “glue” LiPON (cathode protection and 0.1 to 2.5 (e.g., 1.0) 0.21electrolyte) LiCoO₂ (cathode) 8.0 to 40 (e.g., 12.5) 7.00 ½ cathodecollector 1.5 and up (e.g., 6.25) 2.59 screen/mesh/etched foil Totals(e.g., 74.5) 32.37

In some embodiments, the cathode material layers include 31.25 micronsLiCoO₂ in each repeat structure (50% of screen volume) at 80% packing,and 95% electrical utilization corresponds to 1.63 mAhr/cm²/repeat unit,and 6.22 mWhr/cm²/repeat unit at 3.8 V average discharge voltage. Insome embodiments, the LiCoO₂ is infused with polyPN or other polymerelectrolyte material to enhance the ionic conductivity within thecathode. In some embodiments, the charge storage density equals 218mAhr/cm³; and 50.35 Ahr/kg. In some embodiments, the energy storagedensity equals 835 Whr/liter, and 192 Whr/kg. In some embodiments, each10 cm×6.5 cm×1 repeat unit corresponds to 106 mAhr; 404 mWhr. In someembodiments, a final package 10.8 cm×6.5 cm×1.8 cm houses three sets of80 repeat units each tied in series to deliver 8.5 Ahr in discharge from12.3 V to 9 V.

FIG. 5B is a schematic cross-section view of a series-connectedscreen-cathode-contact lithium-battery 501 of some embodiments of theinvention. This embodiment is substantially similar to that of FIG. 4,except that a metal screening or mesh is laminated to the bottom side offoil 535 (a foil corresponding to foil 110 of FIG. 4), or the bottomside of foil 535 (starting with a foil 110 of FIG. 1A) is selectivelyetched only part-way through to form a foil top side and a bottom sidethat has a mesh-like quality. In some embodiments, this allows greatercontact area to the cathode material 112, which is still completelycovered by LiPON layer 114. In some embodiments, foil-mesh layer 535 isformed by selectively etching a photolithographically-defined areas of ametal foil, but not all the way through. In some embodiments, theoutermost layers are single sided as shown, having a metal face facingoutwards. In other embodiments, all layers 535 are identical one toanother, including the outermost layers (wherein the electrode layersfacing outwards are non-functioning). In some embodiments, the edge ofthe top-most layer 535 is electrically connected (for example, on theright-hand side) to form external cathode current-collector contact 531,and the edge of bottom-most layer 535 is electrically connected (forexample, on the left-hand side) to form external anode current-collectorcontact 532, thus connecting all the cells in series. Each repeat unit530 shows one basic stack layer.

In some embodiments, the thin (0.1 to 1.0 micron) LiPON electrolyteserves as a hard coating at the negative electrode preventing theformation of lithium dendrites. Its use as a coating at the positiveelectrode (i.e., LiCoO₂) doubly ensures that lithium plating at a defectsite will not short the battery. At both electrodes, LiPON also providesan improvement in environmental resistance to water vapor and oxygen.

In some embodiments, the use of a relatively soft solid polymerelectrolyte (SPE) simplifies the construction of cells over a fullhard-electrolyte solid-state (e.g., LiPON only as the electrolyte)design. The soft polymer electrolyte functions as an “electrolyte glue”that allows the positive and negative electrodes to be constructedseparately and adhered to each other later in the assembly process. Insome embodiments, the soft polymer electrolyte is sprayed, squeegeed, orotherwise deposited in liquid form, and later solidified.

Without the LiPON coating, some embodiments using a soft polymerelectrolyte would need sufficient soft polymer electrolyte thickness tohave mechanical rigidity or mechanical strength, which reduces energydensity and increases cell resistance. Without the soft polymerelectrolyte (“electrolyte glue”), LiPON films would need to be perfect(defect free) over very large areas to achieve high-energy cells. Thecombination of the two electrolyte material systems eliminatesshortcomings of either used alone.

Numerous metals can be used as the anode in battery cells of the presentinvention. One common anode metal is lithium. The lithium must beprotected from oxygen and water vapor during manufacturing, assembly,and use of the battery. Zinc is another common anode metal used in someembodiments of the present invention. Zinc is the most electronegativemetal that has good stability and corrosion resistance, with theappropriate inhibitor chemistry, in aqueous solutions. Several possiblemetal-air systems are listed in Table 4 along with a summary of theirtheoretical characteristics.

TABLE 4 Characteristics of metal-air cells. From “Handbook of Batteries,3^(rd) Ed.,” David Linden and Thomas B. Reddy, Eds., Table 38.2,McGraw-Hill Handbooks, New York, 2002. SUMMARY OF OTHER LITHIUM/AIRRESEARCH Electrochemical Theoretical Theoretical Practical equivalentcell specific energy operating Metal of metal, voltage, Valence (ofmetal), voltage, anode Ah/g *V change kWh/kg V Li 3.86 3.4 1 13.0 2.4 Ca1.34 3.4 2 4.6 2.0 Mg 2.20 3.1 2 6.8 1.2-1.4 Al 2.98 2.7 3 8.1 1.1-1.4Zn 0.82 1.6 2 1.3 1.0-1.2 Fe 0.96 1.3 2 1.2 1.0 *Cell voltage withoxygen cathode

Lithium, the lightest alkali metal, has a unique place in batterysystems. Its gravimetric electrochemical equivalence of 3.86 amp-hrs/gis the highest of any metallic anode material. It can be seen from Table3 that lithium has the highest operational voltage and greatesttheoretical specific energy of the metals listed. Using a lithium anodeleads to a very light, high energy density battery. The difficulty withlithium technology is providing practical systems that operate in realworld conditions. It is possible to construct lithium cells utilizing anaqueous electrolyte, but these cells have limited applicability due tocorrosion of the lithium metal anode by water. The lithium anode mayalso corrode from contact with oxygen. A solution to the rapid corrosionof lithium metal anodes in lithium-air cells includes the use of LiPONas a protective barrier and separator in the structure of anorganic-electrolyte lithium cell.

In some embodiments, a cell utilizes a LiPON thin film acting as both aportion of the electrolyte structure and a protective barrier againstmoisture and oxygen corrosion of the lithium metal anode. The structureof thin, flexible, lithium cells lends itself well to high-speedweb-deposition processes, as described in U.S. Pat. No. 6,805,998 (whichis incorporated herein by reference).

In some embodiments, a battery of the present invention (e.g., referencenumbers 100, 300, 400, 500, 600 or 900) is incorporated in an electricaldevice such as a hearing aid, compass, cellular phone, tracking system,scanner, digital camera, portable computer, radio, compact disk player,cassette player, smart card, or other battery-powered device.

In some embodiments, the back (outside) of the cathode is exposed (orcan be exposed, for example, by removing a protective polymer filmlayer) to air, such that oxygen acts as a cathode material. In some suchembodiments, the air cathode battery is a primary battery that cannot berecharged, while in other embodiments, the air cathode battery is asecondary battery that can be recharged.

Other Embodiments of the Invention

One aspect of the invention includes an apparatus including a lithiumanode covered by a LiPON electrolyte/protective layer, alithium-intercalation-material cathode covered by a LiPONelectrolyte/protective layer and a polymer electrolyte materialsandwiched between the LiPON electrolyte/protective layer that coversthe anode and the LiPON electrolyte/protective layer that covers thecathode.

In some embodiments, the cathode includes LiCoO₂.

In some embodiments of the invention, the anode overlays a copper-anodecurrent-collector contact.

Another aspect of the invention includes a method including providing ananode substrate having a conductive anode-current-collector contactlayer thereon, depositing a LiPON electrolyte/barrier layer over theanode-current-collector contact layer, providing a polymer electrolyte,and providing a cathode substrate having a cathode-current-collectorcontact layer, depositing a lithium intercalation material on thecathode current-collector contact layer, depositing a LiPONelectrolyte/barrier layer over the cathode-current-collector contactlayer, and forming a sandwich of the anode substrate and the cathodesubstrate with the polymer electrolyte therebetween. In someembodiments, a structure is provided having a plurality of anodesubstrates and a plurality of cathode substrates with polymerelectrolyte between each pair of anode and cathode substrates.

Another aspect of the invention includes an apparatus that includes asubstrate having an anode current-collector contact, a LiPON electrolyteseparator deposited on the anode current-collector contact, and a platedlayer of lithium anode material between the LiPON and the anodecurrent-collector contact.

In some embodiments, the anode current-collector contact includes copperand the substrate includes a polymer.

Another aspect of the invention includes an apparatus including adeposition station that deposits LiPON onto an anode current-collectorcontact, a plating station that plates lithium onto the anodecurrent-collector contact to form an anode substrate, acathode-deposition station that deposits a cathode material onto asubstrate and deposits LiPON onto the cathode material to form a cathodesubstrate, and an assembly station that assembles the anode substrate tothe cathode substrate using a polymer electrolyte material sandwichedbetween the cathode substrate and the anode substrate.

In some embodiments of the invention, the deposition station comprisessputter deposition of LiPON.

In some embodiments, the LiPON is deposited onto the anodecurrent-collector contact with a thickness of between about 0.1 micronsand about 1 micron. In some embodiments, the anode's LiPON layer is lessthan 0.1 microns thick. In some embodiments, this LiPON layer is about0.1 microns. In some embodiments, this LiPON layer is about 0.2 microns.In some embodiments, this LiPON layer is about 0.3 microns. In someembodiments, this LiPON layer is about 0.4 microns. In some embodiments,this LiPON layer is about 0.5 microns. In some embodiments, this LiPONlayer is about 0.6 microns. In some embodiments, this LiPON layer isabout 0.7 microns. In some embodiments, this LiPON layer is about 0.8microns. In some embodiments, this LiPON layer is about 0.9 microns. Insome embodiments, this LiPON layer is about 1.0 microns. In someembodiments, this LiPON layer is about 1.1 microns. In some embodiments,this LiPON layer is about 1.2 microns. In some embodiments, this LiPONlayer is about 1.3 microns. In some embodiments, this LiPON layer isabout 1.4 microns. In some embodiments, this LiPON layer is about 1.5microns. In some embodiments, this LiPON layer is about 1.6 microns. Insome embodiments, this LiPON layer is about 1.7 microns. In someembodiments, this LiPON layer is about 1.8 microns. In some embodiments,this LiPON layer is about 1.9 microns. In some embodiments, this LiPONlayer is about 2.0 microns. In some embodiments, this LiPON layer isabout 2.1 microns. In some embodiments, this LiPON layer is about 2.2microns. In some embodiments, this LiPON layer is about 2.3 microns. Insome embodiments, this LiPON layer is about 2.4 microns. In someembodiments, this LiPON layer is about 2.5 microns. In some embodiments,this LiPON layer is about 2.6 microns. In some embodiments, this LiPONlayer is about 2.7 microns. In some embodiments, this LiPON layer isabout 2.8 microns. In some embodiments, this LiPON layer is about 2.9microns. In some embodiments, this LiPON layer is about 3 microns. Insome embodiments, this LiPON layer is about 3.5 microns. In someembodiments, this LiPON layer is about 4 microns. In some embodiments,this LiPON layer is about 4.5 microns. In some embodiments, this LiPONlayer is about 5 microns. In some embodiments, this LiPON layer is about5.5 microns. In some embodiments, this LiPON layer is about 6 microns.In some embodiments, this LiPON layer is about 7 microns. In someembodiments, this LiPON layer is about 8 microns. In some embodiments,this LiPON layer is about 7 microns. In some embodiments, this LiPONlayer is about 9 microns. In some embodiments, this LiPON layer is about10 microns. In some embodiments, this LiPON layer is more than 10microns.

In some embodiments, the LiPON is deposited onto the cathodecurrent-collector contact with a thickness of between about 0.1 micronsand about 1 micron. In some embodiments, the cathode's LiPON layer isless than 0.1 microns thick. In some embodiments, this UPON layer isabout 0.1 microns. In some embodiments, this LiPON layer is about 0.2microns. In some embodiments, this UPON layer is about 0.3 microns. Insome embodiments, this LiPON layer is about 0.4 microns. In someembodiments, this LiPON layer is about 0.5 microns. In some embodiments,this LiPON layer is about 0.6 microns. In some embodiments, this LiPONlayer is about 0.7 microns. In some embodiments, this LiPON layer isabout 0.8 microns. In some embodiments, this LiPON layer is about 0.9microns. In some embodiments, this LiPON layer is about 1.0 microns. Insome embodiments, this LiPON layer is about 1.1 microns. In someembodiments, this LiPON layer is about 1.2 microns. In some embodiments,this LiPON layer is about 1.3 microns. In some embodiments, this LiPONlayer is about 1.4 microns. In some embodiments, this LiPON layer isabout 1.5 microns. In some embodiments, this LiPON layer is about 1.6microns. In some embodiments, this UPON layer is about 1.7 microns. Insome embodiments, this LiPON layer is about 1.8 microns. In someembodiments, this LiPON layer is about 1.9 microns. In some embodiments,this LiPON layer is about 2.0 microns. In some embodiments, this LiPONlayer is about 2.1 microns. In some embodiments, this LiPON layer isabout 2.2 microns. In some embodiments, this LiPON layer is about 2.3microns. In some embodiments, this LiPON layer is about 2.4 microns. Insome embodiments, this LiPON layer is about 2.5 microns. In someembodiments, this LiPON layer is about 2.6 microns. In some embodiments,this LiPON layer is about 2.7 microns. In some embodiments, this LiPONlayer is about 2.8 microns. In some embodiments, this LiPON layer isabout 2.9 microns. In some embodiments, this LiPON layer is about 3microns. In some embodiments, this LiPON layer is about 3.5 microns. Insome embodiments, this LiPON layer is about 4 microns. In someembodiments, this LiPON layer is about 4.5 microns. In some embodiments,this LiPON layer is about 5 microns. In some embodiments, this LiPONlayer is about 5.5 microns. In some embodiments, this LiPON layer isabout 6 microns. In some embodiments, this LiPON layer is about 7microns. In some embodiments, this LiPON layer is about 8 microns. Insome embodiments, this LiPON layer is about 7 microns. In someembodiments, this LiPON layer is about 9 microns. In some embodiments,this LiPON layer is about 10 microns. In some embodiments, this LiPONlayer is more than 10 microns.

In some embodiments, the plating station performs electroplating atdensities of about 0.9 mA/cm² and voltage of about 40 mV at 0.6 mAbetween a lithium counterelectrode and the plated lithium of the anode.

In some embodiments of the invention, during a precharge of the anode,the lithium is conducted through a liquid propylene carbonate/LiPF₆ (orother suitable lithium salt) electrolyte solution and the LiPONbarrier/electrolyte layer for the lithium to be wet-bath plated onto theanode connector or conduction layer (e.g., copper foil or a copper layeron an SiO₂ or polymer substrate.

FIG. 6A is a perspective view of an electrode 600 having ahard-electrolyte-covered current collector with a plating mask 119. Insome embodiments, a starting substrate such as 721 shown in FIG. 7B hasits metal layer 720 (e.g., copper) photolithographically defined to formpatterned metal layer 620 having contact pad 629, used for plating (suchas shown in FIG. 6C) and for connecting to the external electricalconductor in the finished battery. In some embodiments, on top ofpatterned metal layer 620 is a patterned (e.g., photolithographically)hard electrolyte layer 624 (e.g., such as a hard electrolyte layer 124described in FIG. 1C, but with some of its lateral edges removed). Insome embodiments, an optional mask layer 119 is formed and/or patternedover the metal via between the main body of patterned metal layer 620(which will be plated with lithium through patterned hard electrolytelayer 624 (e.g., LiPON)). In some embodiments, mask 119 prevents lithiumfrom plating on the via, thus leaving sealed the interface betweenpatterned hard electrolyte layer 624 and the metal via (otherwise, watervapor or air could cause the lithium plated in this area to corrode,leaving a gap that could cause more corrosion of the main body of thelithium on patterned metal layer 620. Because the patterned hardelectrolyte layer 624 extends laterally beyond the lateral extent ofpatterned metal layer 620 on the rest of its periphery, no mask isrequired in those areas, since the lithium will not plate there and thesealed interface between patterned hard electrolyte layer 624 and theunderlying non-conductive substrate remains intact and sealed.

FIG. 6B is a perspective view of another electrode 601 having ahard-electrolyte-covered current collector with a plating mask 119. Insome embodiments such as shown here, the entire substrate surface ismetal, so a mask 119 is deposited and/or patterned over the outerperiphery of hard electrolyte layer 124 (e.g., LiPON), mask 119 with aninterior opening 129 through which lithium will plate through the LiPONlayer 124 to most of the central portion of the face of substrate 120(e.g., a metal foil). In some embodiments, mask 119 is a photoresistlayer that is patterned and left in place during plating. In otherembodiments, mask 119 is another material (such as deposited SiO₂) thatis patterned using photoresist, which is then removed. In still otherembodiments, mask 119 is a material (such as SiO₂) that is depositeddirectly on the metal substrate 120, and is patterned using photoresistthat is then removed before deposition of the hard electrolyte layer 124(e.g., LiPON), thus preventing lithium from plating around the periphery(i.e., the mask 119 is under the LiPON, in some embodiments).

FIG. 6C is a perspective view of a plating system 610. In someembodiments, one or more electrodes 600 and/or electrodes 601 arepartially or completely submerged in a liquid electrolyte 606 (e.g.,propylene carbonate and/or ethylene carbonate with dissolved LiPF₆ orother suitable electrolyte). In some embodiments, a sacrificial block oflithium 605 is kept submerged in the electrolyte 606, and a suitableplating voltage is applied between the lithium block 605 andelectrode(s) 600 and/or 601. In some embodiments, the contact pad 629 iskept out of the liquid to prevent lithium from plating there.

FIGS. 7A, 7B, 7C, 7D, 7E, and 7F are schematic cross-sectional views ofthe fabrication (shown as a series 700 of operations) of an atomic levelmatrix of copper and copper oxides as cathodes on a substrate of someembodiments of the invention. FIG. 7A shows a cross-section view of thestarting substrate 710 (e.g., silicon, alumina, stainless steel,aluminum, or polymer, or a composite of different materials). In someembodiments, an aluminum-foil substrate (or other metal that couldspontaneously alloy with lithium and thereby degrade performance of thebattery) or an insulator or non-conductor (such as silicon or polymer,which does not conduct the electricity from the battery) is coated withcopper or nickel (or other metal that conducts electricity and does notreadily alloy with lithium and thereby helps maintain performance of thebattery).

In some embodiments, a cathode starting material contains no lithium(e.g., a copper foil, screening, or insulator coated with a copperconduction layer, then coated with a high-surface area carbon orCu_(x)O_(x) (which has a high volumetric energy density) or othermaterial useful as a lithium-battery electrode, optionally infused withpolyPN). In some embodiments, (see FIG. 7B) a metal layer 720 (e.g.,copper, nickel, or other suitable metal that does not readily alloy withlithium during charging or discharging of the battery) is deposited(e.g., by sputtering copper with no oxygen) on one or more major faces(e.g., the top and/or bottom surfaces shown in the figures) of asubstrate 710 (e.g., a silicon wafer optionally having an SiO₂insulation layer on one or both sides, an alumina or glass wafer, or apolymer film), to form a metal-coated substrate 721. In someembodiments, metal-coated substrate 721 can be used as the currentcollector base (rather than metal foil 111 or 121) for either the anodeor cathode of any of the above-described embodiments.

In some embodiments, the starting substrate includes a plurality ofmetal layers (e.g., aluminum or copper moisture-barrier layers)alternating with a smoothing layer (e.g., spun-on photoresist orpolyurethane) between each pair of metal layers to form a barrier stack(e.g., see U.S. patent application Ser. No. 11/031,217 filed Jan. 6,2005, entitled “LAYERED BARRIER STRUCTURE HAVING ONE OR MORE DEFINABLELAYERS AND METHOD”, which is incorporated herein by reference), whereinthe top-most metal layer of this stack is a metal that (unlike aluminum)does not readily alloy with lithium during battery charging ordischarging (e.g., a metal such as copper). Such a moisture-barrierstack is particularly useful for sealing a substrate that transmits somemoisture and/or oxygen over time (e.g., a polymer film substrate such aspolyethylene or Kapton™), where the barrier stack.

For some embodiments using a lithium-free starting cathode, copper isthen is sputtered in a partial O₂ atmosphere onto metal-coated substrate721 (in some embodiments, the concentration of oxygen is increased overtime such that the first material deposited is mostly copper, andgradually the material includes more and more oxygen in thecopper-copper-oxide matrix) in argon (e.g., forming an atomic-scalemixture of copper, Cu₄O in layer 722 (see FIG. 7C), Cu₂O in layer 724(see FIG. 7D), Cu⁺O⁻ and/or CuO in layer 728 (see FIG. 7E), or asuccession of the copper substrate 720, then mostly Cu₄O in layer 722,then mostly Cu₂O in layer 724, then Cu⁺O⁻ and then CuO in layer 728and/or an atomic-scale matrix of copper and copper oxides). In someembodiments, a layer of hard electrolyte 714 (see FIG. 7F), such asLiPON, is deposited across the finished cathode material.

FIGS. 8A, 8B, 8C, 8D, and 8E are schematic cross-sectional views of thefabrication (shown as a series 800 of operations) of an atomic levelmatrix of copper and copper oxides as cathodes on a copper-foilsubstrate of some embodiments of the invention. In some embodiments,(see FIG. 8A) a copper foil 711 or film is the starting material. Insome embodiments, the starting foil is sputtered with argon to clean thesurface(s) to be used for cathodes (e.g., the top and/or bottom surfacesshown), then copper is sputtered in a partial O₂ atmosphere (in someembodiments, the concentration of oxygen is increased over time suchthat the first material deposited is mostly copper, and gradually thematerial includes more and more oxygen in the copper-copper-oxidematrix) in argon (e.g., forming an atomic-scale mixture of copper, Cu₄O722 (see FIG. 8B), Cu₂O 724 (see FIG. 8C), Cu⁺O⁻ and/or CuO 728 (seeFIG. 8D), or a succession of the copper substrate 720, then mostly Cu₄O722, then mostly Cu₂O 724, then Cu⁺O⁻ and then CuO 728 and/or anatomic-scale matrix of copper and copper oxides). In some embodiments, alayer of hard electrolyte 714 (see FIG. 8E) such as LiPON is depositedacross the finished cathode material.

In some such embodiments, the copper metal spreads through the copperoxides (which intercalate lithium, in some embodiments), providingbetter electrical conductivity as the lithium migrates in and out of thecathode. In some embodiments, the anode is precharged by electroplatinglithium through the LiPON electrolyte that has been deposited thereon.

In other embodiments, one or more copper oxides and/or copper powder arepowder-pressed onto a copper substrate or screen (i.e., the cathodeconduction layer). In still other embodiments, an ink, having one ormore copper oxides and/or copper powder, is printed, sprayed,doctor-bladed, or otherwise deposited on the cathode conduction layer.In some embodiments of the invention, the cathode material is chargedwith lithium that is conducted through a liquid propylenecarbonate/LiPF₆ electrolyte solution and the LiPON barrier/electrolytelayer for the lithium to be plated onto/into the cathode material and/orconnector or conduction layer.

FIG. 9 is a schematic cross-section view of a parallel-connectedfoil-substrate-cathode -current-collector contact thin-film battery 900of some embodiments of the invention. Battery 900 includes two cellsconnected in parallel, where two-sided anode current collector 120 hasanode material 122 (e.g., lithium metal) that has been electroplatedthrough hard electrolyte layers 124 (e.g., LiPON) on both sides ofcentral current collector layer 120 (e.g., a metal foil or metal-coatedpolymer film), as defined by masks 119. In some embodiments, two cathodecurrent collectors 110 each have cathode material 112 (e.g., LiCoO₂)deposited and photolithographically patterned and covered with hardelectrolyte layers 124 (e.g., LiPON). Pinhole 992 in hard electrolytelayer 124 and/or pinhole 991 in hard electrolyte layer 124 would causefailures of a typical single-layer electrolyte battery, but in thepresent invention, the pinholes do not align (e.g., vertically in thefigure) with one another, and, in some embodiments, are filled with thesoft polymer electrolyte 130, which acts to fill such holes andautomatically “heal” the battery. Other details of this battery are asdescribed above for FIG. 3.

FIG. 10A is a schematic cross-section view of an encapsulatedsurface-mount single-cell micro-battery device 1000 of some embodimentsof the invention (other embodiments use stacks of cells as describedabove). In some embodiments, a silicon wafer substrate has a pluralityof such cells fabricated on it, and is diced apart to form siliconsubstrate 1011 having a metal current collector 1010 on its surface,which then has cathode material 112 and hard electrolyte layer 114deposited thereon to form the cathode component. A foil anode componenthaving foil substrate 120, anode metal 122, and hard electrolyte layer124 is then laminated to the cathode component using a soft polymerelectrolyte glue 130. This battery is then connected to a lead framehaving cathode connector 1051 and anode connector 1052 and encapsulatedin encapsulant material 1050, and the leads formed as gull-wing leads asshown or bent into J-shaped leads that curl under the package.Surface-mount-device 1000 can then be soldered to a circuit board toprovide small amounts of battery power to other components on thecircuit board (such as real-time clocks or timers, or staticrandom-access memories, RFID circuits, and the like). In otherembodiments, a plurality of foil battery cells is used instead andencapsulated to form a surface-mount chip-like battery having highercurrent and/or higher voltage capabilities.

FIG. 10B is a perspective view of the outside of encapsulatedsurface-mount micro-battery device 1000 (described above in FIG. 10A),of some embodiments of the invention. In some embodiments, a stack offoil battery cells (e.g., such as those described in FIG. 3, FIG. 4,FIG. 5A, and/or FIG. 5B, and, in some embodiments, with or without asilicon wafer substrate) is encapsulated in this form factor to create asurface-mount chip-like battery having higher current and/or highervoltage capabilities.

FIG. 11 is a flow chart of a method 1100 for making a battery cellaccording to some embodiments of the invention. In some embodiments,method 1100 includes providing 1110 a first sheet (e.g., 121) thatincludes an anode material and a hard electrolyte layer covering theanode material, providing 1112 a second sheet (e.g., 111) having acathode material and a hard electrolyte layer covering the cathodematerial, and sandwiching 1114 a soft (e.g., polymer) electrolytematerial between the hard electrolyte layer of the first sheet and thehard electrolyte layer of the second sheet. Some embodiments of themethod 1100 further include the functions shown in FIG. 12.

FIG. 12 is a flow chart of a method 1200 for making a stacked batteryaccording to some embodiments of the invention. In some embodiments,method 1200 includes performing 1210 the method 1100 of FIG. 11,providing 1212 a third sheet that includes an anode material and a hardelectrolyte layer covering the anode material, providing a fourth sheetthat includes a cathode material and a hard electrolyte layer coveringthe cathode material, sandwiching 1216 a polymer electrolyte materialbetween the hard electrolyte layer covering the anode material of thethird sheet and the hard electrolyte layer covering the cathode materialof the fourth sheet, and between the hard electrolyte layer covering theanode material of the first sheet and the hard electrolyte layercovering the cathode material of the fourth sheet.

FIG. 13 is a perspective exploded view of information-processing system1300 (such as a laptop computer) using battery device 1330 (which, invarious embodiments, is any one or more of the battery devices describedherein). For example, in various exemplary embodiments,information-processing system 1300 embodies a computer, workstation,server, supercomputer, cell phone, automobile, washing machine,multimedia entertainment system, or other device. In some embodiments,packaged circuit 1320 includes a computer processor that is connected tomemory 1321, power supply (energy-storage device 1330), input system1312 (such as a keyboard, mouse, and/or voice-recognition apparatus),input-output system 1313 (such as a CD or DVD read and/or writeapparatus), input-output system 1314 (such as a diskette or othermagnetic media read/write apparatus), output system 1311 (such as adisplay, printer, and/or audio output apparatus), wireless communicationantenna 1340, and packaged within enclosure having a top shell 1310,middle shell 1315, and bottom shell 1316. In some embodiments,energy-storage device 1330 is deposited (e.g., as vapors formingthin-film layers in a vacuum deposition station) or laminated (aspartially assembled electrode films) as thin-film layers directly on andsubstantially covering one or more surfaces of the enclosure (i.e., topshell 1310, middle shell 1315, and/or bottom shell 1316).

FIG. 14 shows an information-processing system 1400 having a similarconfiguration to that of FIG. 13. In various exemplary embodiments,information-processing system 1400 embodies a pocket computer, personaldigital assistant (PDA) or organizer, pager, Blackberry™-type unit, cellphone, GPS system, digital camera, MP3 player-type entertainment system,and/or other device. In some embodiments, packaged circuit 1420 includesa computer processor that is connected to memory 1421, power-supplybattery device 1430, input system 1412 (such as a keyboard, joystick,and/or voice-recognition apparatus), input/output system 1414 (such as aportable memory card connection or external interface), output system1411 (such as a display, printer, and/or audio output apparatus),wireless communication antenna 1440, and packaged within enclosurehaving a top shell 1410 and bottom shell 1416. In some embodiments,battery device 1430 (which, in various embodiments, is any one or moreof the battery devices described herein) is deposited as film layersdirectly on and substantially covering one or more surfaces of theenclosure (i.e., top shell 1410 and/or bottom shell 1416).

In some embodiments, at least one of the hard electrolyte layers is aglass-like layer that conducts lithium ions. In some such embodiments,at least one of the hard electrolyte layers includes LiPON. In someembodiments, the first hard electrolyte layer and the second hardelectrolyte layer are both LiPON. In some such embodiments, each of thehard electrolyte layers is formed by sputtering from a LiPON source ontosubstrates having one or more electrode materials. In some suchembodiments, each of the hard electrolyte layers is formed by sputteringfrom a lithium phosphate source in a nitrogen atmosphere onto substrateshaving one or more electrode materials. In some embodiments, each of thehard electrolyte layers is formed by sputtering from a lithium phosphatesource in a nitrogen atmosphere, using an ion-assist voltage, ontosubstrates having one or more electrode materials.

In some embodiments, the soft electrolyte layer includes one or morepolymers having a gel-like consistency at room temperatures.

In some embodiments, the soft layer includes a polyphosphazene polymer.In some such embodiments, the soft layer includes co-substituted linearpolyphosphazene polymers. In some such embodiments, the soft layerincludes polyphosphazene polymers having a gel-like consistency at roomtemperatures. In some such embodiments, the soft layer includes MEEP(poly[bis(2-(T-methoxyethoxy ethoxy)phosphazene]).

In some embodiments, the soft-electrolyte layer is formed by depositingsoft-electrolyte material onto the hard-electrolyte layer on thepositive electrode, depositing soft-electrolyte material onto thehard-electrolyte layer on the negative electrode, and pressing thesoft-electrolyte material on the positive electrode and thesoft-electrolyte material on the negative electrode against each other.

In some embodiments, the soft layer includes a polymer matrix infusedwith a liquid and/or gel electrolyte material (e.g., polyPN). In somesuch embodiments, the polymer matrix is formed by waffle embossing(micro-embossing to leave raised structures, e.g., about 0.1 micronshigh to about 5 microns high: in some embodiments, about 0.1 microns,about 0.2 microns, about 0.3 microns, about 0.4 microns, about 0.5microns, about 0.6 microns, about 0.7 microns, about 0.8 microns, about0.9 microns, about 1.0 microns, about 1.2 microns, about 1.4 microns,about 1.6 microns, about 1.8 microns, about 2.0 microns, about 2.2microns, about 2.4 microns, about 2.6 microns, about 2.8 microns, about3.0 microns, about 3.5 microns, about 4 microns, about 4.5 microns,about 5 microns, about 6 microns, about 7 microns, about 8 microns,about 9 microns, or about 10 microns high) a heated polymer materialonto at least one of the positive electrode and the negative electrode.In some such embodiments, the waffle embossing forms a pattern of dots.In some such embodiments, the waffle embossing forms a pattern of lines.In some such embodiments, the waffle embossing forms atwo-directional/two-dimensional pattern of lines (e.g., in someembodiments, intersecting lines forming squares, triangles, hexagons,and/or the like, while in other embodiments, non-intersecting geometricpatterns such as circles, squares, triangles, and/or the like). In otherembodiments, a one-directional pattern of lines is microembossed in onedirection on the positive electrode and in another direction on thenegative electrode.

In some embodiments, the soft electrolyte layer includes a thin (e.g.,0.5 to 5.0 microns thick) polymer sponge or screen (e.g., apolypropylene sponge) infused with a liquid and/or gel electrolytematerial (e.g., polyPN) and placed between the two hard electrolytelayers.

In some such embodiments, the soft-electrolyte layer is formed bydepositing a thin soft-electrolyte layer onto the hard electrolyte layeron the positive electrode, depositing a thin soft-electrolyte layer ontothe hard electrolyte layer on the negative electrode, and pressing thesoft electrolyte layer on the positive electrode and the softelectrolyte layer on the negative electrode against each other. In somesuch embodiments, at least one of the thin soft-electrolyte layers isformed by doctor blading. In some such embodiments, at least one of thethin soft-electrolyte layers is formed by spraying. In some suchembodiments, at least one of the thin soft-electrolyte layers is formedby silk-screening. In some such embodiments, at least one of the thinsoft-electrolyte layers is formed by printing.

In some embodiments, the battery includes a positive electrode thatincludes a LiCoO₂ layer deposited on a copper current-collector layer,about 1 micron of LiPON deposited on the LiCoO₂ layer, a layer ofbetween about 1 micron and three microns of polyphosphazene/lithium-saltelectrolyte material, and about 1 micron of LiPON on the negativeelectrode. In some embodiments, the negative electrode includes a coppercurrent collector onto which LiPON is deposited and that is prechargedby wet plating lithium onto the copper current collector through theLiPON layer. In some embodiments, the layer ofpolyphosphazene/lithium-salt electrolyte material is formed bydepositing about 1 micron of polyphosphazene/lithium-salt electrolytematerial on the LiPON deposited on the positive electrode, depositingabout 1 micron of polyphosphazene/lithium-salt electrolyte material onthe LiPON on the negative electrode and contacting thepolyphosphazene/lithium-salt electrolyte material on the positiveelectrode to the polyphosphazene/lithium-salt electrolyte material onthe negative electrode. In some such embodiments, the contactingincludes pressing between rollers.

Some embodiments of the invention include an apparatus that includes abattery cell having a positive electrode, a negative electrode, and anelectrolyte structure therebetween, wherein the electrolyte structureincludes a soft electrolyte layer and at least one hard electrolytelayer.

In some embodiments, the electrolyte structure includes a hardelectrolyte layer on the negative electrode, and the soft electrolytelayer is sandwiched between the positive electrode and the hardelectrolyte layer on the negative electrode. In some such embodiments,the invention omits the hard electrolyte covering on the positiveelectrode.

In some embodiments, the soft electrolyte layer includes apolyphosphazene. In some embodiments, the soft electrolyte layerincludes MEEP. In some embodiments, the soft electrolyte layer alsoincludes a metal salt, such as LiPF6, LiBF4, LiCF3SO4, CF3SO3Li (lithiumtrifluoromethanesulfonate, also called triflate), lithiumbisperfluoroethanesulfonimide, lithium (Bis)Trifluoromethanesulfonimide, or the like or a mixture or two or moresuch salts, for example.

In some embodiments, the electrolyte structure includes a hardelectrolyte layer on the positive electrode and a hard electrolyte layeron the negative electrode, and the soft electrolyte layer is sandwichedbetween the hard electrolyte layer on the positive electrode and thehard electrolyte layer on the negative electrode. In some embodiments,the thicknesses of the hard electrolyte layer on the positive electrodeand of the hard electrolyte layer on the negative electrode are eachabout one micron or less. In some embodiments, the thicknesses of thehard electrolyte layer on the positive electrode and of the hardelectrolyte layer on the negative electrode are each about 0.5 micronsor less. In some embodiments, the thickness of the soft electrolytelayer is about three microns or less. In some embodiments, the thicknessof the soft electrolyte layer is about two microns or less. In someembodiments, the thickness of the soft electrolyte layer is about onemicron or less.

In some embodiments, the hard electrolyte layer on the positiveelectrode includes is substantially the same material as the hardelectrolyte layer on the negative electrode. In some embodiments, thehard electrolyte layer on the positive electrode includes issubstantially the same thickness as the hard electrolyte layer on thenegative electrode.

In some embodiments, the hard electrolyte layer on the positiveelectrode includes LiPON and the hard electrolyte layer on the negativeelectrode includes UPON.

In some embodiments, the soft electrolyte layer includes a gel.

In some embodiments, the soft electrolyte layer includes a gel thatincludes a polyvinylidene difluoride (PVdF), propylene carbonate, and alithium salt. PVdF is a polymer that does not conduct lithium ions, thatis, lithium salts will not dissolve in PVdF. However, PVdF can beswollen with a liquid such as propylene carbonate in which a lithiumsalt has been dissolved. The gel that results can be used as a softelectrolyte.

Some embodiments further include an encapsulating material surroundingthe battery cell, and one or more electrical leads connecting from thebattery cell to an exterior of the encapsulating material.

Some embodiments further include an electronic device and a housingholding the electrical device, wherein the battery cell is within thehousing and supplies power to the electronic device.

Some embodiments of the invention include a method that includesproviding a positive electrode component, providing a negative electrodecomponent, coating at least the negative electrode component with a hardelectrolyte layer, and forming a battery cell using the positiveelectrode component, the negative electrode component that is coatedwith the hard electrolyte layer, and a soft electrolyte layer inbetween.

Some embodiments of the method further include coating the positiveelectrode component with a hard electrolyte layer, wherein anelectrolyte structure of the battery cell includes the hard electrolytelayer on the negative electrode, the hard electrolyte layer on thepositive electrode, and the soft electrolyte layer which is sandwichedbetween the hard electrolyte layer on the positive electrode and thehard electrolyte layer on the negative electrode.

In some embodiments of the method, the electrolyte structure includes ahard electrolyte layer on the positive electrode and a hard electrolytelayer on the negative electrode, and the soft electrolyte layer issandwiched between the hard electrolyte layer on the positive electrodeand the hard electrolyte layer on the negative electrode.

In some embodiments of the method, the hard electrolyte layer on thepositive electrode includes LiPON and the hard electrolyte layer on thenegative electrode includes LiPON.

In some embodiments of the method, the soft electrolyte layer includes apolyphosphazene and a lithium salt. In some embodiments, the softelectrolyte layer includes MEEP and a lithium salt. In some embodiments,the lithium salt includes LiPF6, LiBF4, LiCF3SO4, CF3SO3Li (lithiumtrifluoromethanesulfonate, also called triflate), lithiumbisperfluoroethanesulfonimide, lithium (Bis)Trifluoromethanesulfonimide, or the like or a mixture or two or moresuch salts, for example.

Some embodiments of the invention include an apparatus that includes apositive electrode component coated with a hard electrolyte layer, anegative electrode component coated with a hard electrolyte layer, andelectrolyte means for connecting the hard electrolyte layer on thenegative electrode component to the hard electrolyte layer on thepositive electrode component to form a battery cell.

In some embodiments, the means for connecting further includes means forfixing defects in one or more of the hard electrolyte layers.

In some embodiments, the hard electrolyte layer on the positiveelectrode includes LiPON and the hard electrolyte layer on the negativeelectrode includes LiPON.

In some embodiments, the means for connecting includes MEEP. In someembodiments, the means for connecting includes a polyphosphazene and alithium salt. In some embodiments, the means for connecting includesMEEP and a lithium salt. In some embodiments, the lithium salt includesLiPF6, LiBF4, LiCF3SO4, CF3SO3Li (lithium trifluoromethanesulfonate,also called triflate), lithium bisperfluoroethanesulfonimide, lithium(Bis) Trifluoromethanesulfonimide, or the like or a mixture or two ormore such salts, for example.

Some embodiments further include an encapsulating material surroundingthe battery cell, and one or more electrical leads connecting from thebattery cell to an exterior of the encapsulating material.

Some embodiments further include an electronic device, wherein thebattery cell supplies power to at least a portion of the electronicdevice.

Some embodiments of the invention include an apparatus that includes afirst battery cell having a negative electrode, a positive electrode,and an electrolyte structure, wherein the negative electrode includes ananode material and a LiPON layer covering at least a portion of thenegative electrode, the positive electrode includes a cathode materialand a UPON layer covering at least a portion of the positive electrode,and the electrolyte structure includes a polymer electrolyte materialsandwiched between the LiPON layer of the negative electrode and theLiPON layer of the positive electrode.

In some embodiments, the cathode material includes LiCoO2 that isdeposited on a positive electrode current-collector material, and theLiPON layer of the positive electrode is deposited on the LiCoO2. Insome such embodiments, the positive electrode current-collector contactmaterial includes a metal mesh around which the cathode material isdeposited.

In some embodiments, the negative electrode includes anegative-electrode current collector made of a metal that does notreadily alloy with lithium during a plating operation, and lithium metalis plated onto the negative-electrode current collector through theLiPON layer covering the negative electrode. In some such embodiments,the metal of the negative-electrode current collector includes copper.In some such embodiments, the negative electrode includes a mask layercovers a periphery of the negative-electrode current collector andlithium metal is plated through the LiPON layer covering the negativeelectrode onto an area of the metal negative-electrode current collectordefined by the mask.

In some embodiments, the negative electrode includes a current-collectormetal layer, and the anode material includes lithium metal deposited onat least one of two major faces of the metal layer that is at leastpartially covered by the LiPON layer of the negative electrode.

In some embodiments, the anode material is deposited on both major facesof the metal layer of the negative electrode, each face at leastpartially covered by the LiPON layer of the negative electrode.

In some embodiments, the positive electrode includes a current-collectormetal layer, and the cathode material is deposited on both major facesof the metal layer and is at least partially covered by the LiPON layer.

In some embodiments, the negative electrode includes a current-collectormetal layer, and the anode material includes lithium metal plated ontoboth major faces of the negative-electrode current-collector metal layerthrough the LiPON layer covering the negative electrode.

In some embodiments, the negative electrode includes a current-collectorcontact foil coated with the LiPON layer of the negative electrode, thelithium anode material includes lithium metal plated onto a first majorface of the current-collector contact foil through the LiPON layercovering the current-collector contact foil, the lithium cathodematerial of a second battery cell is deposited onto a second major faceof the current-collector contact foil of the negative electrode of thefirst battery cell, and the LiPON barrier/electrolyte layer covering thecathode material of the second battery cell is then deposited bysputtering.

In some embodiments, the positive electrode includes a current-collectorfoil, the lithium cathode material is deposited onto both major faces ofthe positive electrode current-collector contact foil, and the LiPONbarrier/electrolyte layer covering the positive electrode is thendeposited by sputtering.

In some embodiments, the positive electrode includes a current-collectorcontact mesh, the lithium cathode material is deposited onto both majorfaces of the cathode current-collector contact mesh, and the LiPONbarrier/electrolyte layer covering the positive electrode is thendeposited by sputtering.

Some embodiments of the invention include a method that includesproviding a first sheet that includes an anode material and a LiPONbarrier/electrolyte layer covering the anode material, providing asecond sheet that includes a cathode material that includes lithium anda LiPON barrier/electrolyte layer covering the cathode material, andsandwiching a polymer electrolyte material between the LiPONbarrier/electrolyte layer covering the anode material of the first sheetand the LiPON barrier/electrolyte layer covering the cathode material ofthe first cathode sheet.

Some embodiments of the method further include providing a third sheetthat includes an anode material and a LiPON barrier/electrolyte layercovering the anode material, providing a fourth sheet that includes acathode material that includes lithium and a LiPON barrier/electrolytelayer covering the cathode material, sandwiching a polymer electrolytematerial between the LiPON barrier/electrolyte layer covering the anodematerial of the third sheet and the LiPON barrier/electrolyte layercovering the cathode material of the fourth sheet, and sandwiching apolymer electrolyte material between the LiPON barrier/electrolyte layercovering the anode material of the first sheet and the LiPONbarrier/electrolyte layer covering the cathode material of the fourthsheet.

In some embodiments of the method, the anode is deposited as a layer ona copper anode current-collector contact layer through a LiPON layer.

In some embodiments of the method, the deposition of a lithium anode isdone by electroplating in a propylene carbonate/LiPF6 electrolytesolution.

In some embodiments of the method, the first sheet includes a cathodematerial on a face opposite the anode material and a LiPONbarrier/electrolyte layer covering the cathode material, and the secondsheet includes an anode material that includes lithium on a faceopposite the cathode material and a LiPON barrier/electrolyte layercovering the anode material, wherein the method further includesproviding a third sheet that includes an anode material that includeslithium and a LiPON barrier/electrolyte layer covering the anodematerial on a first face, and an anode material that includes lithiumand a LiPON barrier/electrolyte layer covering the anode material on asecond face opposite the first face, and sandwiching a polymerelectrolyte material between the UPON barrier/electrolyte layer coveringthe anode material of the first sheet and the LiPON barrier/electrolytelayer covering the cathode material of the third sheet.

Some embodiments of the invention include an apparatus that includes afirst sheet that includes an anode material that includes lithium and aLiPON barrier/electrolyte layer covering the anode material on a firstface of the first sheet, a second sheet that includes a cathode materialthat includes lithium and a LiPON barrier/electrolyte layer covering thecathode material on a second face of the second sheet, and means forpassing ions between the LiPON layer on the first face of the firstsheet and the LiPON layer on the second face of the second sheet to forma first battery cell.

In some embodiments, the first sheet includes a LiPON layer on a secondface of the first sheet, and the apparatus further includes a thirdsheet that includes an anode material that includes lithium and a LiPONbarrier/electrolyte layer covering the anode material on a first face ofthe third sheet, a fourth sheet that includes a cathode material thatincludes lithium and a LiPON barrier/electrolyte layer covering thecathode material on a second face of the fourth sheet and a cathodematerial that includes lithium and a LiPON barrier/electrolyte layercovering the cathode material on a first face of the fourth sheet, meansfor passing ions between the LiPON layer on the first face of the thirdsheet and the LiPON layer on the second face of the fourth sheet to forma second battery cell, and means for passing ions between the LiPONlayer on the second face of the first sheet and the LiPON layer on thefirst face of the fourth sheet to form a third battery cell.

In some embodiments, the first sheet includes a copper anodecurrent-collector layer, and the anode material includes lithiumdeposited as a lithium-metal layer on the copper anode current-collectorlayer through the LiPON layer of the first sheet.

In some embodiments, a periphery of the lithium-metal layer is definedby a mask, and the deposition of a lithium anode is done byelectroplating in a liquid propylene carbonate/LiPF6 electrolytesolution.

In some embodiments, the first sheet includes a cathode material on asecond face opposite the anode material on the first face and a LiPONbarrier/electrolyte layer covering the cathode material of the firstsheet, and the apparatus further includes a third sheet having an anodematerial that includes lithium and a LiPON barrier/electrolyte layercovering the anode material on a first face of the third sheet, andmeans for passing ions between the LiPON layer on the second face of thefirst sheet and the LiPON layer on the first face of the third sheet toform a series-connected pair of battery cells.

Some embodiments of the invention include an apparatus that includes adeposition station that deposits a hard electrolyte layer on a negativeelectrode component, a deposition station that deposits a hardelectrolyte layer on a positive electrode component, and a laminationstation that laminates the hard electrolyte layer on the negativeelectrode component to the hard electrolyte layer on the positiveelectrode component with a soft electrolyte layer therebetween to form acomposite electrolyte structure.

Some embodiments further include a deposition station that deposits asoft electrolyte layer on the hard electrolyte layer on the negativeelectrode component. In some embodiments, the soft electrolyte layerincludes a polyphosphazene.

Some embodiments further include a deposition station that deposits asoft electrolyte layer on the hard electrolyte layer on the negativeelectrode component, and a deposition station that deposits a softelectrolyte layer on the hard electrolyte layer on the positiveelectrode component.

In some embodiments, the deposition station that deposits the hardelectrolyte layer on the positive electrode deposits a material thatincludes LiPON, the deposition station that deposits the hardelectrolyte layer on the negative electrode component deposits amaterial that includes LiPON, and the deposition station that depositsthe soft electrolyte layer deposited on the hard electrolyte layer onthe positive electrode component and the deposition station thatdeposits the soft electrolyte layer on the hard electrolyte layer on thenegative electrode deposits a material that includes a polyphosphazeneand a lithium salt. In some embodiments, the soft electrolyte layerincludes MEEP.

In some embodiments, the deposition station that deposits the hardelectrolyte layer on the positive electrode deposits a material thatincludes LiPON and the deposition station that deposits the hardelectrolyte layer on the negative electrode deposits a material thatincludes LIPON.

Some embodiments further include a deposition station that deposits aLiCoO2 layer on the positive electrode before the hard electrolyte layeris deposited on the positive electrode component.

Some embodiments further include an electroplating station that plates alithium metal layer on the negative electrode through the hardelectrolyte layer after the hard electrolyte layer is deposited on thenegative electrode component.

Some embodiments further include a patterning station that deposits aphotoresist layer and patterns a mask that defines an area on thenegative electrode component to which a lithium metal layer can beformed.

Some embodiments of the invention include a method that includesproviding a positive electrode component, providing a negative electrodecomponent, depositing a hard electrolyte layer on the negative electrodecomponent, depositing a hard electrolyte layer on a positive electrodecomponent, and laminating the hard electrolyte layer on the negativeelectrode to the hard electrolyte layer on the positive electrode with asoft electrolyte layer therebetween to form a composite electrolytestructure.

In some embodiments of the method, the depositing of the hardelectrolyte layer on the positive electrode component includessputtering a LiPON layer, and the depositing of the hard electrolytelayer on the negative electrode component includes sputtering a LiPONlayer.

In some embodiments of the method, the soft electrolyte layer includes apolyphosphazene and a lithium salt.

Some embodiments further include depositing a soft electrolyte layer onthe hard electrolyte layer on the negative electrode component, anddepositing a soft electrolyte layer on the hard electrolyte layer on apositive electrode component, and wherein the laminating presses thesoft electrolyte layer on the hard electrolyte layer on the negativeelectrode component against the soft electrolyte layer on the hardelectrolyte layer on the positive electrode component.

In some embodiments, the depositing of the soft electrolyte layer on thehard electrolyte layer on the negative electrode component includesdoctor blading.

In some embodiments, the depositing of the soft electrolyte layer on thehard electrolyte layer on the negative electrode component includesspraying soft electrolyte material in a liquid form.

In some embodiments, the depositing of the soft electrolyte layer on thehard electrolyte layer on the positive electrode component includes spincoating soft electrolyte material in a liquid form.

Some embodiments of the invention include an apparatus that includes asource of a positive electrode component, a source of a negativeelectrode component, means for depositing a hard electrolyte layer onthe negative electrode component, means for depositing a hardelectrolyte layer on a positive electrode component, and means forlaminating the hard electrolyte layer on the negative electrode to thehard electrolyte layer on the positive electrode with a soft electrolytelayer therebetween to form a composite electrolyte structure.

Some embodiments further include means for depositing a soft electrolytelayer on the hard electrolyte layer on the negative electrode component,and means for depositing a soft electrolyte layer on the hardelectrolyte layer on a positive electrode component, and wherein themeans for laminating presses the soft electrolyte layer on the hardelectrolyte layer on the negative electrode component against the softelectrolyte layer on the hard electrolyte layer on the positiveelectrode component.

In some embodiments, the hard electrolyte layer deposited on thepositive electrode component includes LiPON and the hard electrolytelayer deposited on the negative electrode component includes LiPON.

In some embodiments, the soft electrolyte layers include apolyphosphazene and a lithium salt.

In some embodiments, the soft electrolyte layers include MEEP.

Some embodiments of the invention include an apparatus that includes abattery cell having an anode, a cathode, and an electrolyte structure,wherein the anode includes an anode material that, when the battery cellis charged, includes lithium and a LiPON barrier/electrolyte layercovering at least a portion of the anode, the cathode includes a cathodematerial that includes lithium and a LiPON barrier/electrolyte layercovering at least a portion of the cathode, and the electrolytestructure includes a polymer electrolyte material sandwiched between theLiPON barrier/electrolyte layer covering the anode and the LiPONbarrier/electrolyte layer covering the cathode.

In some embodiments of the apparatus, the cathode material includesLiCoO₂ deposited on a cathode-current-collector contact material, andthen the LiPON barrier/electrolyte layer covering the cathode isdeposited.

In some embodiments of the apparatus, the cathode material includesLiCoO₃ deposited on a cathode-current-collector contact material, andthen the UPON barrier/electrolyte layer covering the cathode isdeposited.

In some embodiments of the apparatus, the lithium anode material isplated onto a copper anode current-collector contact or currentcollector through LiPON barrier/electrolyte layer covering the anode.

In some embodiments of the apparatus, the anode material is deposited onboth major faces of a metal sheet at least partially covered by theLiPON barrier/electrolyte layer.

In some embodiments of the apparatus, the cathode material is depositedon both major faces of a metal sheet and is at least partially coveredby the LiPON barrier/electrolyte layer.

In some embodiments of the apparatus, the cathode current-collectorcontact material includes a metal mesh around which the cathode materialis deposited.

In some embodiments of the apparatus, the lithium anode material isplated onto both major faces of an anode current-collector contact foilthrough LiPON barrier/electrolyte layer covering the anodecurrent-collector contact layer.

In some embodiments of the apparatus, the lithium anode material isplated onto a first major face of a current-collector contact foilthrough LiPON barrier/electrolyte layer covering the current-collectorcontact foil the lithium cathode material is deposited onto a secondmajor face of the current-collector contact foil, and the LiPONbarrier/electrolyte layer covering the cathode is then deposited bysputtering.

In some embodiments of the apparatus, the lithium cathode material isdeposited onto both major faces of a cathode current-collector contactfoil, and the LiPON barrier/electrolyte layer covering the cathode isthen deposited by sputtering.

In some embodiments of the apparatus, the lithium cathode material isdeposited onto both major faces of a cathode current-collector contactmesh, and the LiPON barrier/electrolyte layer covering the cathode isthen deposited by sputtering.

In some embodiments, another aspect of the invention includes a methodthat includes providing a first sheet that includes an anode materialthat includes lithium and a LiPON barrier/electrolyte layer covering theanode material, providing a second sheet that includes a cathodematerial that includes lithium and a LiPON barrier/electrolyte layercovering the cathode material, and sandwiching a polymer electrolytematerial between the LiPON barrier/electrolyte layer covering the anodematerial of the first sheet and the LiPON barrier/electrolyte layercovering the cathode material of the second sheet.

Some embodiments of the method further include providing a third sheetthat includes an anode material that includes lithium and a LiPONbarrier/electrolyte layer covering the anode material, providing afourth sheet that includes a cathode material that includes lithium anda LiPON barrier/electrolyte layer covering the cathode material,sandwiching a polymer electrolyte material between the LiPONbarrier/electrolyte layer covering the anode material of the third sheetand the UPON barrier/electrolyte layer covering the cathode material ofthe fourth sheet, and sandwiching a polymer electrolyte material betweenthe LiPON barrier/electrolyte layer covering the anode material of thefirst sheet and the LiPON barrier/electrolyte layer covering the cathodematerial of the fourth sheet.

In some embodiments of the method, the anode is deposited as a layer ona copper anode current-collector contact layer through a LiPON layer.

In some embodiments of the method, the deposition of a lithium anode isdone by electroplating in a propylene carbonate/LiPF₆ electrolytesolution.

In some embodiments of the method, the first sheet includes a cathodematerial on a face opposite the anode material and a LiPONbarrier/electrolyte layer covering the cathode material, and the secondsheet includes an anode material that includes lithium on a faceopposite the cathode material on the second sheet and a LiPONbarrier/electrolyte layer covering the anode material, and the methodfurther includes providing a third sheet that includes an anode materialthat includes lithium and a LiPON barrier/electrolyte layer covering theanode material on a first face, and an anode material that includeslithium and a LiPON barrier/electrolyte layer covering the anodematerial on a second face opposite the first face, and sandwiching apolymer electrolyte material between the LiPON barrier/electrolyte layercovering the anode material of the first sheet and the LiPONbarrier/electrolyte layer covering the cathode material of the thirdsheet.

In some embodiments, another aspect of the invention includes anapparatus that includes a first sheet that includes an anode materialthat includes lithium and a LiPON barrier/electrolyte layer covering theanode material, a second sheet that includes a cathode material thatincludes lithium and a LiPON barrier/electrolyte layer covering thecathode material, and means for sandwiching a polymer electrolytematerial between the LiPON barrier/electrolyte layer covering the anodematerial of the first sheet and the LiPON barrier/electrolyte layercovering the cathode material of the second sheet.

Some embodiments of this apparatus include a third sheet that includesan anode material that includes lithium and a LiPON barrier/electrolytelayer covering the anode material, a fourth sheet that includes acathode material that includes lithium and a LiPON barrier/electrolytelayer covering the cathode material, means for sandwiching a polymerelectrolyte material between the LiPON barrier/electrolyte layercovering the anode material of the third sheet and the LiPONbarrier/electrolyte layer covering the cathode material of the fourthsheet, and means for sandwiching a polymer electrolyte material betweenthe LiPON barrier/electrolyte layer covering the anode material of thefirst sheet and the LiPON barrier/electrolyte layer covering the cathodematerial of the fourth sheet.

In some embodiments, the first sheet includes a cathode material on aface opposite the anode material and a UPON barrier/electrolyte layercovering the cathode material, and the second sheet includes an anodematerial that includes lithium on a face opposite the cathode materialand a LiPON barrier/electrolyte layer covering the anode material, andthe apparatus further includes a third sheet that includes an anodematerial that includes lithium and a LiPON barrier/electrolyte layercovering the anode material on a first face, and an anode material thatincludes lithium and a LiPON barrier/electrolyte layer covering theanode material on a second face opposite the first face, and means forsandwiching a polymer electrolyte material between the LiPONbarrier/electrolyte layer covering the anode material of the first sheetand the LiPON barrier/electrolyte layer covering the cathode material ofthe third sheet.

It is to be understood that the above description is intended to beillustrative, and not restrictive. Although numerous characteristics andadvantages of various embodiments as described herein have been setforth in the foregoing description, together with details of thestructure and function of various embodiments, many other embodimentsand changes to details will be apparent to those of skill in the artupon reviewing the above description. The scope of the invention should,therefore, be determined with reference to the appended claims, alongwith the full scope of equivalents to which such claims are entitled. Inthe appended claims, the terms “including” and “in which” are used asthe plain-English equivalents of the respective terms “comprising” and“wherein,” respectively. Moreover, the terms “first,” “second,” and“third,” etc., are used merely as labels, and are not intended to imposenumerical requirements on their objects.

1. A method comprising: providing an anode component comprising a firstsheet that includes an anode material and a first LiPON layer coveringthe anode material and having randomly spaced defects; providing acathode component comprising a second sheet that includes a cathodematerial that includes lithium and a second LiPON layer covering thecathode material and having randomly spaced defects; and sandwiching apolymer electrolyte material between the LiPON layer covering the anodematerial of the first sheet and the LiPON layer covering the cathodematerial of the second sheet, wherein the polymer electrolyte materialincludes a gel and at least partially fills and fixes the randomlyspaced defects in the first and second LiPON layers.
 2. The method ofclaim 1, further comprising: providing a third sheet that includes ananode material and a third LiPON layer covering the anode material;providing a fourth sheet that includes a cathode material that includeslithium and a fourth LiPON layer covering the cathode material;sandwiching a polymer electrolyte material between the LiPON layercovering the anode material of the third sheet and the LiPON layercovering the cathode material of the fourth sheet; and sandwiching apolymer electrolyte material between the LiPON layer covering the anodematerial of the third sheet and the LiPON layer covering the cathodematerial of the second sheet.
 3. The method of claim 1, wherein theanode material of the first sheet is deposited as a lithium-metal layeron a copper anode-current-collector layer through the LiPON layer. 4.The method of claim 3, wherein the deposition of a lithium anode is doneby electroplating in a propylene carbonate/lithium-salt electrolytesolution prior to assembling the cell.
 5. The method of claim 1, whereinthe first sheet includes a cathode material on a face opposite the anodematerial and a LiPON layer covering the cathode material, and the secondsheet includes an anode material on a face opposite the cathode materialand a LiPON layer covering the anode material; the method furthercomprising: providing a third sheet that includes an anode material anda LiPON layer covering the anode material on a first face, and a cathodematerial that includes lithium and a LiPON layer covering the cathodematerial on a second face opposite the first face; and sandwiching thepolymer electrolyte material between the LiPON layer covering the anodematerial of the third sheet and the UPON layer covering the cathodematerial of the second sheet.
 6. The method of claim 1, wherein thepolymer electrolyte layer includes a polyvinylidene difluoride,propylene carbonate, and a lithium salt.
 7. The method of claim 1,further comprising the step of laminating two or more battery cellstogether to form a laminated battery device.
 8. The method of claim 1,wherein the laminated battery device comprises a stack of two-sidedanode current collectors and two-sided cathode current collectors thatare connected in parallel.
 9. The method of claim 1, wherein thelaminated battery device comprises a stack of two-sided anode currentcollectors and two-sided cathode current collectors that are connectedin series.
 10. The method of claim 1, wherein the polymer electrolytelayer is an adhesive that provides a structural connection between theLiPon layers.
 11. The method of claim 1, wherein the anode componentcomprises a current collector onto which is deposited a cathodematerial.
 12. The method of claim 1, wherein the anode component furthercomprises a current collector, and wherein a layer of lithium is formedas an active portion of the cathode component after assembly of thebattery cell.
 13. The method of claim 1, wherein the polymer electrolytelayer is sticky.
 14. The method of claim 1, wherein the polymerelectrolyte layer comprises polyvinylidene difluoride, propylenecarbonate, and a lithium salt.
 15. The method of claim 1, wherein thepolymer electrolyte layer comprises MEEP.
 16. The method of claim 1,wherein the negative electrode component includes a negative-electrodecurrent collector made of a metal that does not readily alloy withlithium during a plating operation, and lithium metal is plated onto thenegative-electrode current collector through the LiPON layer on thenegative electrode component.
 17. The method of claim 1, wherein thepolymer electrolyte layer comprises a polyphosphazene and a lithiumsalt.